Compositions of ethylene/alpha-olefin multi-block interpolymer for elastic films and laminates

ABSTRACT

This invention relates to polyolefin compositions. In particular, the invention pertains to elastic polymer compositions that can be more easily processed on cast film lines, extrusion lamination or coating lines. The compositions of the present invention preferably comprise an elastomeric polyolefin resin and a high pressure low density type resin.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. application Ser. No.11/376,956, filed Mar. 15, 2006 and U.S. application Ser. No.11/377,333, filed Mar. 15, 2006. This application also claims priorityunder 35 USC § 120 from U.S. Application Ser. No. 11/376,835, filed Mar.15, 2006. For purposes of United States patent practice, the contents ofthe above referenced applications are herein incorporated by referencein their entirety.

FIELD OF THE INVENTION

This invention relates to blends of ethylene/a-olefin multi-blockinterpolymer compositions and styrenic block copolymers havingsuitability for elastic compositions with improved processability. Inone aspect, this invention relates to films made from blends ofethylene/a-olefin multi-block interpolymer compositions and styrenicblock copolymers. In another aspect, this invention relates to filamentsand fibers made from blends of ethylene/a-olefin multi-blockinterpolymer compositions and styrenic block copolymers. In yet anotheraspect, this invention relates to laminates comprising filaments,fibers, films, or combinations thereof made from blends ofethylene/a-olefin multi-block interpolymer compositions and styrenicblock copolymers. In still yet another aspect, this invention relates toarticles fabricated using films, fibers, filaments, laminates, orcombinations thereof made using blends of ethylene/a-olefin multi-blockinterpolymer compositions and styrenic block copolymers. Thecompositions have elastic performance, improved heat resistance, andother desirable characteristics.

BACKGROUND AND SUMMARY OF THE INVENTION

Styrenic block copolymers, such as SEBS (polystyrene-saturatedpolybutadiene-polystyrene), SBS (polystyrene-polybutadiene-polystyrene),SEPS (polystyrene-saturated polyisoprene-polystyrene), SIS(polystyrene-polyisoprene-polystyrene), and SEPSEP are known in the art.They exhibit excellent physical properties, such as elasticity andflexibility. However, they often cannot be readily processed on typicalpolyolefin processing equipment, without the need for flow enhancers andother processing aids. Upon formulation with such materials, end-useproperties such as tensile strength and heat resistance can suffer.Furthermore, they can suffer from thermal instability such ascross-linking (i.e. SBS) and scission (i.e. SIS).

Ethylene/a-olefin multi-block interpolymer compositions are readilyprocessible using typical polyolefin processing equipment. They exhibitdesirable end-use properties such as high heat resistance and hightensile strength. However, ethylene/α-olefin multi-block interpolymercompositions are typically are not as flexible and elastic as the mostelastic styrenic block copolymers when used at high strains (i.e.>100%).

It would be desirable to have a thermoplastic elastomer compositionwhich exhibits excellent physical properties, such as elasticity andflexibility, while at the same time being readily processible usingtypical polyolefin processing equipment.

Elastomeric compositions have found particular use in elastic films andfibers. They can be used by themselves, but are more commonly used inlaminated structure wherein the substrate is a nonwoven fabric. Theelastic film or fiber imparts elasticity to the nonwoven laminates. Suchelastic nonwoven laminate materials have found use in the hygiene andmedical market particularly in such applications as elastic diaper tabs,side panels of training pants, leg gathers, feminine hygiene articles,swim pants, incontinent wear, veterinary products, protective clothing,bandages, items of health care such as surgeon's gowns, surgical drapes,sterilization wrap, wipes, and the like. These materials may also finduse in other nonwoven applications including but are not limited tofilters (gas and liquid), automotive and marine protective covers, homefurnishing such as bedding, carpet underpaddings, wall coverings, floorcoverings, window shades, scrims etc.

Elastomeric films can be made in a number of ways known to those ofordinary skill in the art. Single or multi-layer elastic films arepossible. Such processes can include bubble extrusion and biaxialorientation processes, as well as tenter frame techniques. In order tofacilitate elasticity, the elastic film is usually employed singly or asa layer, in the case of multi-layer films. As many elastic compositionstend to be sticky and hence difficult to process or poor in hand feel,at least one non-sticky/non-tacky material may be used to comprise atleast a portion of the film surface to mitigate this effect.Alternatively, various additives and modifiers such (i.e. slip agents,anti-block etc.)may also be employed.

Elastomeric fibers or filaments can be made in a number of ways known tothose of ordinary skill in the art. Monofilament, bicomponent,multicomponent, islands-in-the-sea, crescent, side-by-side and otherconfigurations known to those of ordinary skill in the art are suitablefor use with the inventive composition. Like films, elastic fibers alsotend to be sticky and hence difficult to process or poor in hand feel.At least one non-sticky/non-tacky material may be used to comprise atleast a portion of the film or fiber surface to mitigate this effect.Alternatively, various additives and modifiers such (i.e. slip agents,anti-block etc.) mentioned above may also be employed.

Elastomeric compositions are often used for their retractive force. Theyare commonly used in various forms including fibers, film, laminates andfabric. When used in an article, the retractive force of the elastomerprovides the “holding force” of the structure. For example, in healthand hygiene articles such as infant diapers, training pants, and adultincontinence articles, the elastomers are commonly used in laminatestructures. These laminate structures help to maintain fit of thearticle to the body. Body heat can result in the decrease of the holdingforce of the elastomer over time (measured as stress-relaxation) whichcan translate to loosening and eventual sagging of the article resultingin a decrease in fit. Styrenic block copolymers and their formulationsused in these structures can suffer from excessive stress-relaxation andconsequently articles fabricated using these materials can sagunacceptably in end-use. Accordingly, it is a goal to reduce the amountof stress-relaxation (increase in heat resistance) of the elastomer.This phenomenon is a known problem and has been described previously inthe art. Such art includes but is not limited to WO9829248A1,WO0058541A1, US20020052585A1, US20040127128A1, U.S. Pat. No.6,916,750B2, U.S. Pat. No. 6,547,915B2, U.S. Pat. No. 6,323,389B1, U.SPat. No. 6207237B1, U.S. Pat. No. 6,187,425B1, U.S. Pat. No. 5,332,613A,U.S. Pat. No. 5,288,791A, U.S. Pat. No. 5,260,126A, U.S. Pat. No.5169706A, GB2335427A, and WO2004037141A1.

The compositions suitable for use in elastic films and laminatescomprise a polymer blend comprising at least one ethylene/a-olefininterpolymer, wherein the ethylene/α-olefin interpolymer:

(a) has a Mw/Mn (Mw denotes weight averaged molecular weight; Mn denotesnumber averaged molecular weight) from about 1.7 to about 3.5, at leastone melting point, Tm, in degrees Celsius, and a density, d, ingrams/cubic centimeter, wherein the numerical values of Tm and dcorrespond to the relationship:Tm>−2002.9+4538.5(d)−2422.2(d)²; or

(b) has a Mw/Mn from about 1.7 to about 3.5, and is characterized by aheat of fusion, ΔH in J/g, and a delta quantity, ΔT, in degrees Celsiusdefined as the temperature difference between the tallest DSC peak andthe tallest CRYSTAF peak, wherein the numerical values of ΔT and ΔH havethe following relationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g,wherein the CRYSTAF peak is determined using at least 5 percent of thecumulative polymer, and if less than 5 percent of the polymer has anidentifiable CRYSTAF peak, then the CRYSTAF temperature is 30° C.; or

(c) is characterized by an elastic recovery, Re, in percent at 300percent strain and 1 cycle measured with a compression-molded film ofthe ethylene/α-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of Re and d satisfy thefollowing relationship when ethylene/α-olefin interpolymer issubstantially free of a cross-linked phase:Re>1481-1629(d); or

(d) has a molecular fraction which elutes between 40° C. and 130° C.when fractionated using TREF, characterized in that the fraction has amolar comonomer content of at least 5 percent higher than that of acomparable random ethylene interpolymer fraction eluting between thesame temperatures, wherein said comparable random ethylene interpolymerhas the same comonomer(s) and has a melt index, density, and molarcomonomer content (based on the whole polymer) within 10 percent of thatof the ethylene/α-olefin interpolymer; or

(e) has a storage modulus at 25° C., G′(25° C.), and a storage modulusat 100° C., G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.)is in the range of about 1:1 to about 9:1.

and, at least one styrenic block copolymer;

wherein the ethylene/α-olefin interpolymer has a density of from about0.855 to about 0.878 g/cc and a melt index (I₂) of from about 0.5 g/10min. to about 20 g/10 min.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the melting point/density relationship for the inventivepolymers (represented by diamonds) as compared to traditional randomcopolymers (represented by circles) and Ziegler-Natta copolymers(represented by triangles).

FIG. 2 shows plots of delta DSC-CRYSTAF as a function of DSC MeltEnthalpy for various polymers. The diamonds represent randomethylene/octene copolymers; the squares represent polymer examples 1-4;the triangles represent polymer examples 5-9; and the circles representpolymer Examples 10-19. The “X” symbols represent polymer ComparativeExamples A*-F*.

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms made from inventive interpolymers(represented by the squares andcircles) and traditional copolymers (represented by the triangles whichare various AFFINITY® polymers). The squares represent inventiveethylene/butene copolymers; and the circles represent inventiveethylene/octene copolymers.

FIG. 4 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus TREF elution temperature ofthe fraction for the polymer of Example 5 (represented by the circles)and comparative polymer Comparative Examples E* and F* (represented bythe “X” symbols). The diamonds represent traditional randomethylene/octene copolymers.

FIG. 5 is a plot of octene content of TREF fractionatedethylene/1-octene copolymer fractions versus TREF elution temperature ofthe fraction for the polymer of Example 5 (curve 1) and for polymerComparative Examples F* (curve 2). The squares represent polymerComparative Examples F*; and the triangles represent Example 5.

FIG. 6 is a graph of the log of storage modulus as a function oftemperature for comparative ethylene/1-octene copolymer (curve 2) andpropylene/ethylene copolymer (curve 3) and for two ethylene/1-octeneblock copolymers of the invention made with differing quantities ofchain shuttling agent (curves 1).

FIG. 7 shows a plot of TMA (1 mm) versus flex modulus for some inventivepolymers (represented by the diamonds), as compared to some knownpolymers. The triangles represent various VERSIFY® polymers; the circlesrepresent various random ethylene/styrene copolymers; and the squaresrepresent various AFFINITY® polymers.

FIG. 8 is plot of natural log ethylene mole fraction for randomethylene/α-olefin copolymers as a function of the inverse of DSC peakmelting temperature or ATREF peak temperature. The filled squaresrepresent data points obtained from random homogeneously branchedethylene/α-olefin copolymers in ATREF; and the open squares representdata points obtained from random homogeneously branchedethylene/α-olefin copolymers in DSC. “P” is the ethylene mole fraction;“T” is the temperature in Kelvin.

FIG. 9 is a plot constructed on the basis of the Flory equation forrandom ethylene/α-olefin copolymers to illustrate the definition of“block index.” “A” represents the whole, perfect random copolymer; “B”represents a pure “hard segment”; and “C” represents the whole, perfectblock copolymer having the same comonomer content as “A”. A, B, and Cdefine a triangular area within which most TREF fractions would fall.

FIG. 10 is a representation of a normal DSC profile for an inventivepolymer.

FIG. 11 is a weighted DSC profile obtained by converting FIG. 14.

FIG. 12 is a ¹³C NMR spectrum of Polymer 19A.

FIG. 13 shows tensile recovery of two-component blends containingComponent A (i.e., KRATON® G1652, a SEBS) and Component B (i.e.,AFFINITY® EG8100 or inventive Polymer 19a, 19b or 19i). The cyclesrepresent blends containing KRATON® G1652 and AFFINITY® EG8100 (i.e.,Comparative Examples Y1-Y5 having respectively 0%, 25%, 50%, 75% and100% of AFFINITY® EG8100). The diamonds represent blends containingKRATON® G1652 and inventive Polymer 19a (i.e., Examples 34-37 havingrespectively 25%, 50%, 75% and 100% of Polymer 19a). The trianglesrepresent the blends containing KRATON® G1652 and inventive Polymer 19b(i.e., Examples 38-41 having respectively 25%, 50%, 75% and 100% ofPolymer 19b). The squares represent blends containing KRATON® G1652 andinventive Polymer 19i (i.e., Examples 42-45 having respectively 25%,50%, 75% and 100% of Polymer 19i).

FIG. 14 shows heat resistance properties (i.e., TMA temperatures) oftwo-component blends containing Component A (i.e., KRATON® G1652, aSEBS) and Component B (i.e., AFFINITY® EG8100 or inventive Polymer 19a,19b or 19i). The cycles represent blends containing KRATON® G1652 andAFFINITY® EG8100 (i.e., Comparative Examples Y1-Y5 having respectively0%, 25%, 50%, 75% and 100% of AFFINITY® EG8100). The diamonds representblends containing KRATON® G1652 and inventive Polymer 19a (i.e.,Examples 34-37 having respectively 25%, 50%, 75% and 100% of Polymer19a). The triangles represent the blends containing KRATON® G1652 andinventive Polymer 19b (i.e., Examples 38-41 having respectively 25%,50%, 75% and 100% of Polymer 19b). The squares represent blendscontaining KRATON® G1652 and inventive Polymer 19i (i.e., Examples 42-45having respectively 25%, 50%, 75% and 100% of Polymer 19i).

FIG. 15 shows the effect of composition on permanent set after 300%deformation using the 300% hysteresis test.

FIG. 16 shows the effect of composition on permanent set after 300%deformation using the 300% hysteresis test.

DETAILED DESCRIPTION OF THE INVENTION

General Definitions

The following terms shall have the given meaning for the purposes ofthis invention:

By “neck-in” is meant the reduction in a film web width as it isextruded from a die and which will be caused by a combination ofswelling and surface tension effects as the material leaves the die.Neck-in is measured as the distance between the extrudate web as itemerges from the die minus the width of the extrudate web as it is takenup.

“Polymer” means a polymeric compound prepared by polymerizing monomers,whether of the same or a different type. The generic term “polymer”embraces the terms “homopolymer,” “copolymer,” “terpolymer” as well as“interpolymer.”

“Interpolymer” means a polymer prepared by the polymerization of atleast two different types of monomers. The generic term “interpolymer”includes the term “copolymer” (which is usually employed to refer to apolymer prepared from two different monomers) as well as the term“terpolymer” (which is usually employed to refer to a polymer preparedfrom three different types of monomers). It also encompasses polymersmade by polymerizing four or more types of monomers.

The term “ethylene/α-olefin interpolymer” generally refers to polymerscomprising ethylene and an α-olefin having 3 or more carbon atoms.Preferably, ethylene comprises the majority mole fraction of the wholepolymer, i.e., ethylene comprises at least about 50 mole percent of thewhole polymer. More preferably ethylene comprises at least about 60 molepercent, at least about 70 mole percent, or at least about 80 molepercent, with the substantial remainder of the whole polymer comprisingat least one other comonomer that is preferably an α-olefin having 3 ormore carbon atoms. For many ethylene/octene copolymers, the preferredcomposition comprises an ethylene content greater than about 80 molepercent of the whole polymer and an octene content of from about 10 toabout 15, preferably from about 15 to about 20 mole percent of the wholepolymer. In some embodiments, the ethylene/α-olefin interpolymers do notinclude those produced in low yields or in a minor amount or as aby-product of a chemical process. While the ethylene/α-olefininterpolymers can be blended with one or more polymers, the as producedethylene/α-olefin interpolymers are substantially pure and oftencomprise a major component of the reaction product of a polymerizationprocess.

The ethylene/α-olefin interpolymers comprise ethylene and one or morecopolymerizable α-olefin comonomers in polymerized form, characterizedby multiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties. That is, theethylene/α-olefin interpolymers are block interpolymers, or “olefinblock copolymers”, preferably multi-block interpolymers or copolymers.The terms “interpolymer” and copolymer“are used interchangeably herein.In some embodiments, the multi-block copolymer can be represented by thefollowing formula:(AB)_(n)where n is at least 1, preferably an integer greater than 1, such as 2,3, 4, 5, 10, 15, 20, 30, 40, 50, 60, 70, 80, 90, 100, or higher, “A”represents a hard block or segment and “B” represents a soft block orsegment. Preferably, As and Bs are linked in a substantially linearfashion, as opposed to a substantially branched or substantiallystar-shaped fashion. In other embodiments, A blocks and B blocks arerandomly distributed along the polymer chain. In other words, the blockcopolymers usually do not have a structure as follows.AAA—AA—BBB—BB

In still other embodiments, the block copolymers do not usually have athird type of block, which comprises different comonomer(s). In yetother embodiments, each of block A and block B has monomers orcomonomers substantially randomly distributed within the block. In otherwords, neither block A nor block B comprises two or more sub-segments(or sub-blocks) of distinct composition, such as a tip segment, whichhas a substantially different composition than the rest of the block.

The multi-block polymers typically comprise various amounts of “hard”and “soft” segments. “Hard” segments refer to blocks of polymerizedunits in which ethylene is present in an amount greater than about 95weight percent, and preferably greater than about 98 weight percentbased on the weight of the polymer. In other words, the comonomercontent (content of monomers other than ethylene) in the hard segmentsis less than about 5 weight percent, and preferably less than about 2weight percent based on the weight of the polymer. In some embodiments,the hard segments comprise all or substantially all ethylene. “Soft”segments, on the other hand, refer to blocks of polymerized units inwhich the comonomer content (content of monomers other than ethylene) isgreater than about 5 weight percent, preferably greater than about 8weight percent, greater than about 10 weight percent, or greater thanabout 15 weight percent based on the weight of the polymer. In someembodiments, the comonomer content in the soft segments can be greaterthan about 20 weight percent, greater than about 25 weight percent,greater than about 30 weight percent, greater than about 35 weightpercent, greater than about 40 weight percent, greater than about 45weight percent, greater than about 50 weight percent, or greater thanabout 60 weight percent.

The soft segments can often be present in a block interpolymer fromabout 1 weight percent to about 99 weight percent of the total weight ofthe block interpolymer, preferably from about 5 weight percent to about95 weight percent, from about 10 weight percent to about 90 weightpercent, from about 15 weight percent to about 85 weight percent, fromabout 20 weight percent to about 80 weight percent, from about 25 weightpercent to about 75 weight percent, from about 30 weight percent toabout 70 weight percent, from about 35 weight percent to about 65 weightpercent, from about 40 weight percent to about 60 weight percent, orfrom about 45 weight percent to about 55 weight percent of the totalweight of the block interpolymer. Conversely, the hard segments can bepresent in similar ranges. The soft segment weight percentage and thehard segment weight percentage can be calculated based on data obtainedfrom DSC or NMR. Such methods and calculations are disclosed in U.S.Patent Application Publication No. 2006-0199930A1, entitled“Ethylene/α-Olefin Block Interpolymers”, filed on Mar. 15, 2006, in thename of Colin L. P. Shan, Lonnie Hazlitt, et. al. and assigned to DowGlobal Technologies Inc., the disclosure of which is herein incorporatedby reference in its entirety.

The term “crystalline” if employed, refers to a polymer that possesses afirst order transition or crystalline melting point (Tm) as determinedby differential scanning calorimetry (DSC) or equivalent technique. Theterm may be used interchangeably with the term “semicrystalline”. Theterm “amorphous” refers to a polymer lacking a crystalline melting pointas determined by differential scanning calorimetry (DSC) or equivalenttechnique.

“Elastomeric” means that the material will substantially resume itsoriginal shape after being stretched. To qualify a material aselastomeric and thus suitable for the first component, a 1-cyclehysteresis test to 80% strain was used. For this test, the specimens (6inches long by 1 inch wide) were then loaded lengthwise into a Sintechtype mechanical testing device fitted with pneumatically activatedline-contact grips with an initial separation of 4 inches. Then thesample was stretched to 80% strain at 500 mm/min, and returned to 0%strain at the same speed. The strain at 10 g load upon retraction wastaken as the set. Upon immediate and subsequent extension, the onset ofpositive tensile force was taken as the set strain. The hysteresis lossis defined as the energy difference between the extension and retractioncycle. The load down was the retractive force at 50% strain. In allcases, the samples were measured green or unaged. Strain is defined asthe percent change in sample length divided by the original samplelength (22.25 mm) equal to the original grip separation. Stress isdefined as the force divided by the initial cross sectional area.

The term “multi-block copolymer” or “segmented copolymer” refers to apolymer comprising two or more chemically distinct regions or segments(referred to as “blocks”) preferably joined in a linear manner, that is,a polymer comprising chemically differentiated units which are joinedend-to-end with respect to polymerized ethylenic functionality, ratherthan in pendent or grafted fashion. In a preferred embodiment, theblocks differ in the amount or type of comonomer incorporated therein,the density, the amount of crystallinity, the crystallite sizeattributable to a polymer of such composition, the type or degree oftacticity (isotactic or syndiotactic), regio-regularity orregio-irregularity, the amount of branching, including long chainbranching or hyper-branching, the homogeneity, or any other chemical orphysical property. The multi-block copolymers are characterized byunique distributions of both polydispersity index (PDI or Mw/Mn), blocklength distribution, and/or block number distribution due to the uniqueprocess making of the copolymers. More specifically, when produced in acontinuous process, the polymers desirably possess PDI from 1.7 to 2.9,preferably from 1.8 to 2.5, more preferably from 1.8 to 2.2, and mostpreferably from 1.8 to 2.1. When produced in a batch or semi-batchprocess, the polymers possess PDI from 1.0 to 2.9, preferably from 1.3to 2.5, more preferably from 1.4 to 2.0, and most preferably from 1.4 to1.8.

In the following description, all numbers disclosed herein areapproximate values, regardless whether the word “about” or “approximate”is used in connection therewith. Depending upon the context in whichsuch values are described herein, and unless specifically statedotherwise, such values may vary by 1 percent, 2 percent, 5 percent, or,sometimes, 10 to 20 percent. Whenever a numerical range with a lowerlimit, RL and an upper limit, RU, is disclosed, any number fallingwithin the range is specifically disclosed. In particular, the followingnumbers within the range are specifically disclosed: R═RL+k*(RU-RL),wherein k is a variable ranging from 1 percent to 100 percent with a 1percent increment, i.e., k is 1 percent, 2 percent, 3 percent, 4percent, 5 percent, . . . , 50 percent, 51 percent, 52 percent, . . . ,95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100percent. Moreover, any numerical range defined by two R numbers asdefined in the above is also specifically disclosed.

For purposes of this invention, a film is generally considered to be“elastic” if it has a permanent set of less than 40% as determinedaccording to the following procedure: a 1 inch wide by 6 inch longsample is loaded lengthwise into a Sintech mechanical testing devicefitted with pneumatically activated line-contact grips with an initialseparation of 4 inches. Then, the sample is stretched to 80% strain at500 mm/min and returned to 0% strain at the same speed. The strain at0.05 MPa (megapascals) upon retraction is taken as the permanent set.

“Density” is tested in accordance with ASTM D792.

“Melt Index (12)” is determined according to ASTM D1238 using a weightof 2.16 kg at 190° C. for polymers comprising ethylene as the majorcomponent in the polymer.

“Melt Flow Rate (MFR)” is determined according to ASTM D1238 using aweight of 2.16 kg at 230° C. for polymers comprising propylene as themajor component in the polymer.

“Molecular weight distribution” or MWD is measured by conventional GPCper the procedure described by Williams, T.; Ward, I. M. Journal ofPolymer Science, Polymer Letters Edition (1968), 6(9), 621-624.Coefficient B is 1. Coefficient A is 0.4316.

The term high pressure low density type resin is defined to mean thatthe polymer is partly or entirely homopolymerized or copolymerized inautoclave or tubular reactors at pressures above 14,500 psi (100 MPa)with the use of free-radical initiators, such as peroxides (see forexample U.S. Pat. No. 4,599,392, herein incorporated by reference) andincludes “LDPE” which may also be referred to as “high pressure ethylenepolymer” or “highly branched polyethylene”. The cumulative detectorfraction (CDF) of these materials is greater than about 0.02 formolecular weight greater than 1000000 g/mol as measured using lightscattering. CDF may be determined as described in WO2005/023912 A2,which is herein incorporated by reference for its teachings regardingCDF.

The term “high pressure low density type resin” also includes branchedpolypropylene materials (both homopolymer and copolymer). For thepurposes of the present invention, “branched polypropylene materials”means the type of branched polypropylene materials disclosed inWO2003/08297 1, hereby incorporated by reference in its entirety.

Ethylene/α-Olefin Interpolymers

The ethylene/α-olefin interpolymers used in embodiments of the invention(also referred to as “inventive interpolymer”, “inventive polymer” or“olefin block copolymer”) comprise ethylene and one or morecopolymerizable α-olefin comonomers in polymerized form, characterizedby multiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (block interpolymer),preferably a multi-block copolymer. The ethylene/α-olefin interpolymersare characterized by one or more of the aspects described as follows.

In one aspect, the ethylene/α-olefin interpolymers used in embodimentsof the invention have a Mw/Mn from about 1.7 to about 3.5 and at leastone melting point, Tm, in degrees Celsius and density, d, in grams/cubiccentimeter, wherein the numerical values of the variables correspond tothe relationship:T _(m)>−2002.9+4538.5(d)−2422.2(d)², and preferablyT _(m)≧−6288.1+13141(d)−6720.3(d)², and more preferablyT _(m)≧2858.91−1825.3(d)+1112.8(d)².

Such melting point/density relationship is illustrated in FIG. 1. Unlikethe traditional random copolymers of ethylene/α-olefins whose meltingpoints decrease with decreasing densities, the inventive interpolymers(represented by diamonds) exhibit melting points substantiallyindependent of the density, particularly when density is between about0.87 g/cc to about 0.95 g/cc. For example, the melting point of suchpolymers are in the range of about 110° C. to about 130° C. when densityranges from 0.875 g/cc to about 0.945 g/cc. In some embodiments, themelting point of such polymers are in the range of about 115° C. toabout 125° C. when density ranges from 0.875 g/cc to about 0.945 g/cc.

In another aspect, the ethylene/α-olefin interpolymers comprise, inpolymerized form, ethylene and one or more α-olefins and arecharacterized by a ΔT, in degrees Celsius, defined as the temperaturefor the tallest Differential Scanning Calorimetry (“DSC”) peak minus thetemperature for the tallest Crystallization Analysis Fractionation(“CRYSTAF”) peak and a heat of fusion in J/g, ΔH, and ΔT and ΔH satisfythe following relationships:ΔT>−0.1299(ΔH)+62.81, and preferablyΔT≧−0.1299(ΔH)+64.38, and more preferablyΔT24 −0.1299(ΔH) +65.95,for ΔH up to 130 J/g. Moreover, ΔT is equal to or greater than 48° C.for ΔH greater than 130 J/g. The CRYSTAF peak is determined using atleast 5 percent of the cumulative polymer (that is, the peak mustrepresent at least 5 percent of the cumulative polymer), and if lessthan 5 percent of the polymer has an identifiable CRYSTAF peak, then theCRYSTAF temperature is 30° C., and ΔH is the numerical value of the heatof fusion in J/g. More preferably, the highest CRYSTAF peak contains atleast 10 percent of the cumulative polymer. FIG. 2 shows plotted datafor inventive polymers as well as comparative examples. Integrated peakareas and peak temperatures are calculated by the computerized drawingprogram supplied by the instrument maker. The diagonal line shown forthe random ethylene octene comparative polymers corresponds to theequation ΔT=−0.1299 (ΔH)+62.81.

In yet another aspect, the ethylene/α-olefin interpolymers have amolecular fraction which elutes between 40° C. and 130° C. whenfractionated using Temperature Rising Elution Fractionation (“TREF”),characterized in that said fraction has a molar comonomer contenthigher, preferably at least 5 percent higher, more preferably at least10 percent higher, than that of a comparable random ethyleneinterpolymer fraction eluting between the same temperatures, wherein thecomparable random ethylene interpolymer contains the same comonomer(s),and has a melt index, density, and molar comonomer content (based on thewhole polymer) within 10 percent of that of the block interpolymer.Preferably, the Mw/Mn of the comparable interpolymer is also within 10percent of that of the block interpolymer and/or the comparableinterpolymer has a total comonomer content within 10 weight percent ofthat of the block interpolymer.

In still another aspect, the ethylene/α-olefin interpolymers arecharacterized by an elastic recovery, Re, in percent at 300 percentstrain and 1 cycle measured on a compression-molded film of anethylene/α-olefin interpolymer, and has a density, d, in grams/cubiccentimeter, wherein the numerical values of Re and d satisfy thefollowing relationship when ethylene/α-olefin interpolymer issubstantially free of a cross-linked phase:Re>1481−1629(d); and preferablyRe≧1491−1629(d); and more preferablyRe≧1501−1629(d); and even more preferablyRe≧1511−1629(d).

FIG. 3 shows the effect of density on elastic recovery for unorientedfilms made from certain inventive interpolymers and traditional randomcopolymers. For the same density, the inventive interpolymers havesubstantially higher elastic recoveries.

In some embodiments, the ethylene/α-olefin interpolymers have a tensilestrength above 1 MPa, preferably a tensile strength ≧2 MPa, morepreferably a tensile strength ≧3MPa and/or an elongation at break of atleast 100 percent, more preferably at least 250 percent, highlypreferably at least 500 percent, and most highly preferably at least 750percent at a crosshead separation rate of 11 cm/minute usingmicrotensile ASTM- 1708 geometry.

In still other embodiments, the ethylene/α-olefin interpolymers have a70° C. compression set (ASTM D-3574) of less than 98 percent, preferablyless than 95 percent, and more preferably less than 93 percent.

In some embodiments, the ethylene/α-olefin interpolymers have a heat offusion of less than 85 J/g and/or a pellet blocking strength of equal toor less than 100 pounds/foot (4800 Pa), preferably equal to or less than50 lbs/ft² (2400 Pa), especially equal to or less than 5 lbs/ft² (240Pa), and as low as 0 lbs/ft² (0 Pa).

In other embodiments, the ethylene/α-olefin interpolymers comprise, inpolymerized form, at least 50 mole percent ethylene and have a 70° C.compression set of less than 80 percent, preferably less than 70 percentor less than 60 percent, most preferably less than 40 to 50 percent anddown to close to zero percent.

In some embodiments, the multi-block copolymers possess a PDI fitting aSchultz-Flory distribution rather than a Poisson distribution. Thecopolymers are further characterized as having both a polydisperse blockdistribution and a polydisperse distribution of block sizes andpossessing a most probable distribution of block lengths. Preferredmulti-block copolymers are those containing 4 or more blocks or segmentsincluding terminal blocks. More preferably, the copolymers include atleast 5, 10 or 20 blocks or segments including terminal blocks.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (“NMR”) spectroscopypreferred. Moreover, for polymers or blends of polymers havingrelatively broad TREF curves, the polymer desirably is firstfractionated using TREF into fractions each having an eluted temperaturerange of 10° C. or less. That is, each eluted fraction has a collectiontemperature window of 10° C. or less. Using this technique, said blockinterpolymers have at least one such fraction having a higher molarcomonomer content than a corresponding fraction of the comparableinterpolymer.

In another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks (i.e.,at least two blocks) or segments of two or more polymerized monomerunits differing in chemical or physical properties (blockedinterpolymer), most preferably a multi-block copolymer, said blockinterpolymer having a peak (but not just a molecular fraction) whichelutes between 40° C. and 130° C. (but without collecting and/orisolating individual fractions), characterized in that said peak, has acomonomer content estimated by infra-red spectroscopy when expandedusing a full width/half maximum (FWHM) area calculation, has an averagemolar comonomer content higher, preferably at least 5 percent higher,more preferably at least 10 percent higher, than that of a comparablerandom ethylene interpolymer peak at the same elution temperature andexpanded using a full width/half maximum (FWHM) area calculation,wherein said comparable random ethylene interpolymer has the samecomonomer(s) and has a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer. The full width/half maximum(FWHM) calculation is based on the ratio of methyl to methylene responsearea [CH₃/CH₂] from the ATREF infra-red detector, wherein the tallest(highest) peak is identified from the base line, and then the FWHM areais determined. For a distribution measured using an ATREF peak, the FWHMarea is defined as the area under the curve between T₁ and T₂, where T₁and T₂ are points determined, to the left and right of the ATREF peak,by dividing the peak height by two, and then drawing a line horizontalto the base line, that intersects the left and right portions of theATREF curve. A calibration curve for comonomer content is made usingrandom ethylene/α-olefin copolymers, plotting comonomer content from NMRversus FWHM area ratio of the TREF peak. For this infra-red method, thecalibration curve is generated for the same comonomer type of interest.The comonomer content of TREF peak of the inventive polymer can bedetermined by referencing this calibration curve using its FWHM methyl :methylene area ratio [CH₃/CH₂] of the TREF peak.

Comonomer content may be measured using any suitable technique, withtechniques based on nuclear magnetic resonance (NMR) spectroscopypreferred. Using this technique, said blocked interpolymers have ahigher molar comonomer content than a corresponding comparableinterpolymer.

Preferably, for interpol ymers of ethylene and 1-octene, the blockinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity (−0.2013)T+20.07, more preferably greater than or equal to the quantity (−0.2013)T+21.07, where T is the numerical value of the peak elution temperatureof the TREF fraction being compared, measured in ° C.

FIG. 4 graphically depicts an embodiment of the block interpolymers ofethylene and 1-octene where a plot of the comonomer content versus TREFelution temperature for several comparable ethylene/1-octeneinterpolymers (random copolymers) are fit to a line representing(−0.2013) T+20.07 (solid line). The line for the equation (−0.2013)T+21.07 is depicted by a dotted line. Also depicted are the comonomercontents for fractions of several block ethylene/1-octene interpolymersof the invention (multi-block copolymers). All of the block interpolymerfractions have significantly higher 1-octene content than either line atequivalent elution temperatures. This result is characteristic of theinventive interpolymer and is believed to be due to the presence ofdifferentiated blocks within the polymer chains, having both crystallineand amorphous nature.

FIG. 5 graphically displays the TREF curve and comonomer contents ofpolymer fractions for Example 5 and comparative F to be discussed below.The peak eluting from 40 to 130° C., preferably from 60° C. to 95° C.for both polymers is fractionated into three parts, each part elutingover a temperature range of less than 1 0C. Actual data for Example 5 isrepresented by triangles. The skilled artisan can appreciate that anappropriate calibration curve may be constructed for interpolymerscontaining different comonomers and a line used as a comparison fittedto the TREF values obtained from comparative interpolymers of the samemonomers, preferably random copolymers made using a metallocene or otherhomogeneous catalyst composition. Inventive interpolymers arecharacterized by a molar comonomer content greater than the valuedetermined from the calibration curve at the same TREF elutiontemperature, preferably at least 5 percent greater, more preferably atleast 10 percent greater.

In addition to the above aspects and properties described herein, theinventive polymers can be characterized by one or more additionalcharacteristics. In one aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that said fractionhas a molar comonomer content higher, preferably at least 5 percenthigher, more preferably at least 10, 15, 20 or 25 percent higher, thanthat of a comparable random ethylene interpolymer fraction elutingbetween the same temperatures, wherein said comparable random ethyleneinterpolymer comprises the same comonomer(s), preferably it is the samecomonomer(s), and a melt index, density, and molar comonomer content(based on the whole polymer) within 10 percent of that of the blockedinterpolymer. Preferably, the Mw/Mn of the comparable interpolymer isalso within 10 percent of that of the blocked interpolymer and/or thecomparable interpolymer has a total comonomer content within 10 weightpercent of that of the blocked interpolymer.

Preferably, the above interpolymers are interpolymers of ethylene and atleast one α-olefin, especially those interpolymers having a wholepolymer density from about 0.855 to about 0.935 g/cm³, and moreespecially for polymers having more than about 1 mole percent comonomer,the blocked interpolymer has a comonomer content of the TREF fractioneluting between 40 and 130° C. greater than or equal to the quantity(−0.1356) T+13.89, more preferably greater than or equal to the quantity(-0.1356) T+14.93, and most preferably greater than or equal to thequantity (−0.2013)T+21.07, where T is the numerical value of the peakATREF elution temperature of the TREF fraction being compared, measuredin ° C.

Preferably, for the above interpolymers of ethylene and at least onealpha-olefin, especially those interpolymers having a whole polymerdensity from about 0.855 to about 0.935 g/cm³, and more especially forpolymers having more than about 1 mole percent comonomer, the blockedinterpolymer has a comonomer content of the TREF fraction elutingbetween 40 and 130° C. greater than or equal to the quantity (−0.2013)T+20.07, more preferably greater than or equal to the quantity (−0.2013)T+21.07, where T is the numerical value of the peak elution temperatureof the TREF fraction being compared, measured in ° C.

In still another aspect, the inventive polymer is an olefininterpolymer, preferably comprising ethylene and one or morecopolymerizable comonomers in polymerized form, characterized bymultiple blocks or segments of two or more polymerized monomer unitsdiffering in chemical or physical properties (blocked interpolymer),most preferably a multi-block copolymer, said block interpolymer havinga 1molecular fraction which elutes between 40° C. and 130° C., whenfractionated using TREF increments, characterized in that every fractionhaving a comonomer content of at least about 6 mole percent, has amelting point greater than about 100° C. For those fractions having acomonomer content from about 3 mole percent to about 6 mole percent,every fraction has a DSC melting point of about 110° C. or higher. Morepreferably, said polymer fractions, having at least 1 mol percentcomonomer, has a DSC melting point that corresponds to the equation:Tm≧(−5.5926)(mol percent comonomer in the fraction)+135.90.

In yet another aspect, the inventive polymer is an olefin interpolymer,preferably comprising ethylene and one or more copolymerizablecomonomers in polymerized form, characterized by multiple blocks orsegments of two or more polymerized monomer units differing in chemicalor physical properties (blocked interpolymer), most preferably amulti-block copolymer, said block interpolymer having a molecularfraction which elutes between 40° C. and 130° C., when fractionatedusing TREF increments, characterized in that every fraction that has anATREF elution temperature greater than or equal to about 76° C., has amelt enthalpy (heat of fusion) as measured by DSC, corresponding to theequation:

Heat of fusion (J/gm)≦(3.1718)(ATREF elution temperature in Celsius)−136.58.

The inventive block interpolymers have a molecular fraction which elutesbetween 40° C. and 130° C., when fractionated using TREF increments,characterized in that every fraction that has an ATREF elutiontemperature between 40° C. and less than about 76° C., has a meltenthalpy (heat of fusion) as measured by DSC, corresponding to theequation:Heat of fusion (J/gm) ≦(1.1312)(ATREF elution temperature inCelsius)+22.97.ATREF Peak Comonomer Composition Measurement by Infra-Red Detector

The comonomer composition of the TREF peak can be measured using an IR4infra-red detector available from Polymer Char, Valencia, Spain(http://www.polymerchar.com/).

The “composition mode” of the detector is equipped with a measurementsensor (CH₂) and composition sensor (CH₃) that are fixed narrow bandinfra-red filters in the region of 2800-3000 cm⁻¹. The measurementsensor detects the methylene (CH₂) carbons on the polymer (whichdirectly relates to the polymer concentration in solution) while thecomposition sensor detects the methyl (CH₃) groups of the polymer. Themathematical ratio of the composition signal (CH₃) divided by themeasurement signal (CH₂) is sensitive to the comonomer content of themeasured polymer in solution and its response is calibrated with knownethylene alphα-olefin copolymer standards.

The detector when used with an ATREF instrument provides both aconcentration (CH₂) and composition (CH₃) signal response of the elutedpolymer during the TREF process. A polymer specific calibration can becreated by measuring the area ratio of the CH₃ to CH₂ for polymers withknown comonomer content (preferably measured by NMR). The comonomercontent of an ATREF peak of a polymer can be estimated by applying thereference calibration of the ratio of the areas for the individual CH₃and CH₂ response (i.e. area ratio CH₃/CH₂ versus comonomer content).

The area of the peaks can be calculated using a full width/half maximum(FWHM) calculation after applying the appropriate baselines to integratethe individual signal responses from the TREF chromatogram. The fullwidth/half maximum calculation is based on the ratio of methyl tomethylene response area [CH₃/CH₂] from the ATREF infra-red detector,wherein the tallest (highest) peak is identified from the base line, andthen the FWHM area is determined. For a distribution measured using anATREF peak, the FWHM area is defined as the area under the curve betweenT1 and T2, where T1 and T2 are points determined, to the left and rightof the ATREF peak, by dividing the peak height by two, and then drawinga line horizontal to the base line, that intersects the left and rightportions of the ATREF curve.

The application of infra-red spectroscopy to measure the comonomercontent of polymers in this ATREF-infra-red method is, in principle,similar to that of GPC/FTIR systems as described in the followingreferences: Markovich, Ronald P.; Hazlitt, Lonnie G.; Smith, Linley;“Development of gel-permeation chromatography-Fourier transform infraredspectroscopy for characterization of ethylene-based polyolefincopolymers”, Polymeric Materials Science and Engineering (1991), 65,98-100.; and Deslauriers, P. J.; Rohlfing, D. C.; Shieh, E. T.;“Quantifying short chain branching microstructures in ethylene-1-olefincopolymers using size exclusion chromatography and Fourier transforminfrared spectroscopy (SEC-FTIR)”, Polymer (2002), 43, 59-170, both ofwhich are incorporated by reference herein in their entirety.

The ethylene/α-olefin interpolymers may also be characterized by anaverage block index, ABI, which is greater than zero and up to about 1.0and a molecular weight distribution, M_(w)/M_(n), greater than about1.3. The average block index, ABI, is the weight average of the blockindex (“BI”) for each of the polymer fractions obtained in preparativeTREF (i.e., fractionation of a polymer by Temperature Rising ElutionFractionation) from 20° C. and 110° C., with an increment of 5° C.(although other temperature increments, such as 1° C., 2° C., 10° C.,also can be used):ABI=Σ(w _(i) BI _(i))

where BI_(i) is the block index for the ith fraction of the inventiveethylene/α-olefin interpolymer obtained in preparative TREF, and w_(i)is the weight percentage of the ith fraction. Similarly, the square rootof the second moment about the mean, hereinafter referred to as thesecond moment weight average block index, can be defined as follows.${2^{nd}\quad{moment}\quad{weight}\quad{average}\quad{BI}} = \sqrt{\frac{\sum( {w_{i}( {{BI}_{i} - {ABI}} )}^{2} )}{\frac{( {N - 1} ){\sum w_{i}}}{N}}}$

where N is defined as the number of fractions with BI_(i) greater thanzero. Referring to FIG. 9, for each polymer fraction, BI is defined byone of the two following equations (both of which give the same BIvalue):${BI} = {{\frac{{1/T_{X}} - {1/T_{XO}}}{{1/T_{A}} - {1/T_{AB}}}\quad{or}\quad{BI}} = \frac{{{Ln}\quad P_{X}} - {{Ln}\quad P_{XO}}}{{{Ln}\quad P_{A}} - {{Ln}\quad P_{AB}}}}$where T_(x) is the ATREF (i.e., analytical TREF) elution temperature forthe ith fraction (preferably expressed in Kelvin), P_(x) is the ethylenemole fraction for the ith fraction, which can be measured by NMR or IRas described below. P_(AB) is the ethylene mole fraction of the wholeethylene/α-olefin interpolymer (before fractionation), which also can bemeasured by NMR or IR. T_(A) and P_(A) are the ATREF elution temperatureand the ethylene mole fraction for pure “hard segments” (which refer tothe crystalline segments of the interpolymer). As an approximation orfor polymers where the “hard segment” composition is unknown, the T_(A)and P_(A) values are set to those for high density polyethylenehomopolymer. For calculations performed herein, T_(A) is 372 K, P_(A) is1.

TAB is the ATREF elution temperature for a random copolymer of the samecomposition (having an ethylene mole fraction of PAB) and molecularweight as the inventive copolymer. TAB can be calculated from the molefraction of ethylene (measured by NMR) using the following equation:Ln P _(AB) =α/T _(AB)+βwhere a and β are two constants which can be determined by a calibrationusing a number of well characterized preparative TREF fractions of abroad composition random copolymer and/or well characterized randomethylene copolymers with narrow composition. It should be noted that aand P may vary from instrument to instrument. Moreover, one would needto create an appropriate calibration curve with the polymer compositionof interest, using appropriate molecular weight ranges and comonomertype for the preparative TREF fractions and/or random copolymers used tocreate the calibration. There is a slight molecular weight effect. Ifthe calibration curve is obtained from similar molecular weight ranges,such effect would be essentially negligible. In some embodiments asillustrated in FIG. 8, random ethylene copolymers and/or preparativeTREF fractions of random copolymers satisfy the following relationship:Ln P=−237.83/T _(ATREF)+0.639

The above calibration equation relates the mole fraction of ethylene, P,to the analytical TREF elution temperature, T_(ATREF), for narrowcomposition random copolymers and/or preparative TREF fractions of broadcomposition random copolymers. T_(XO) is the ATREF temperature for arandom copolymer of the same composition (i.e., the same comonomer typeand content) and the same molecular weight and having an ethylene molefraction of P_(x). T_(XO) can be calculated from LnP_(x)=α/T_(XO)+β froma measured P_(X) mole fraction. Conversely, P_(XO) is the ethylene molefraction for a random copolymer of the same composition (i.e., the samecomonomer type and content) and the same molecular weight and having anATREF temperature of T_(X), which can be calculated from LnP_(XO)=α/T_(X)+β using a measured value of T_(X).

Once the block index (BI) for each preparative TREF fraction isobtained, the weight average block index, ABI, for the whole polymer canbe calculated. In some embodiments, ABI is greater than zero but lessthan about 0.4 or from about 0.1 to about 0.3. In other embodiments, ABIis greater than about 0.4 and up to about 1.0. Preferably, ABI should bein the range of from about 0.4 to about 0.7, from about 0.5 to about0.7, or from about 0.6 to about 0.9. In some embodiments, ABI is in therange of from about 0.3 to about 0.9, from about 0.3 to about 0.8, orfrom about 0.3 to about 0.7, from about 0.3 to about 0.6, from about 0.3to about 0.5, or from about 0.3 to about 0.4. In other embodiments, ABIis in the range of from about 0.4 to about 1.0, from about 0.5 to about1.0, or from about 0.6 to about 1.0, from about 0.7 to about 1.0, fromabout 0.8 to about 1.0, or from about 0.9 to about 1.0.

Another characteristic of the inventive ethylene/α-olefin interpolymeris that the inventive ethylene/α-olefin interpolymer comprises at leastone polymer fraction which can be obtained by preparative TREF, whereinthe fraction has a block index greater than about 0.1 and up to about1.0 and the polymer having a molecular weight distribution, M_(w)/M_(n),greater than about 1.3. In some embodiments, the polymer fraction has ablock index greater than about 0.6 and up to about 1.0, greater thanabout 0.7 and up to about 1.0, greater than about 0.8 and up to about1.0, or greater than about 0.9 and up to about 1.0. In otherembodiments, the polymer fraction has a block index greater than about0.1 and up to about 1.0, greater than about 0.2 and up to about 1.0,greater than about 0.3 and up to about 1.0, greater than about 0.4 andup to about 1.0, or greater than about 0.4 and up to about 1.0. In stillother embodiments, the polymer fraction has a block index greater thanabout 0.1 and up to about 0.5, greater than about 0.2 and up to about0.5, greater than about 0.3 and up to about 0.5, or greater than about0.4 and up to about 0.5. In yet other embodiments, the polymer fractionhas a block index greater than about 0.2 and up to about 0.9, greaterthan about 0.3 and up to about 0.8, greater than about 0.4 and up toabout 0.7, or greater than about 0.5 and up to about 0.6.

In addition to an average block index and individual fraction blockindices, the ethylene/α-olefin interpolymers are characterized by one ormore of the properties described as follows.

For copolymers of ethylene and an α-olefin, the inventive polymerspreferably possess (1) a PDI of at least 1.3, more preferably at least1.5, at least 1.7, or at least 2.0, and most preferably at least 2.6, upto a maximum value of 5.0, more preferably up to a maximum of 3.5, andespecially up to a maximum of 2.7; (2) a heat of fusion of 80 J/g orless; (3) an ethylene content of at least 50 weight percent; (4) a glasstransition temperature, T_(g), of less than −25° C., more preferablyless than -30° C., and/or (5) one and only one T_(m).

Further, the inventive polymers can have, alone or in combination withany other properties disclosed herein, a storage modulus, G′, such thatlog (G′) is greater than or equal to 400 kPa, preferably greater than orequal to 1.0 MPa, at a temperature of 100° C. Moreover, the inventivepolymers possess a relatively flat storage modulus as a function oftemperature in the range from 0 to 100° C. (illustrated in FIG. 6) thatis characteristic of block copolymers, and heretofore unknown for anolefin copolymer, especially a copolymer of ethylene and one or moreC₃₋₈ aliphatic α-olefins. (By the term “relatively flat” in this contextis meant that log G′ (in Pascals) decreases by less than one order ofmagnitude between 50 and 100° C., preferably between 0 and 100° C.).

The inventive interpolymers may be further characterized by athermomechanical analysis (TMA) penetration depth of 1 mm at atemperature of at least 90° C. as well as a flexural modulus (ASTMD790A) of from 3 kpsi (20 MPa) to 13 kpsi (90 MPa). Alternatively, theinventive interpolymers can have a thermomechanical analysis penetrationdepth of I mm at a temperature of at least 104° C. as well as a flexuralmodulus of at least 3 kpsi (20 MPa). They may be characterized as havingan abrasion resistance (or volume loss) of less than 90 mm . FIG. 7shows the TMA (1 mm) versus flex modulus for the inventive polymers, ascompared to other known polymers. The inventive polymers havesignificantly better flexibility-heat resistance balance than the otherpolymers.

Additionally, the ethylene/α-olefin interpolymers can have a melt index,I₂, from 0.01 to 2000 g/10 minutes, preferably from 0.01 to 1000 g/10minutes, more preferably from 0.01 to 500 g/10 minutes, and especiallyfrom 0.01 to 100 g/10 minutes. In certain embodiments, theethylene/α-olefin interpolymers have a melt index, I₂, from 0.01 to 10g/10 minutes, from 0.5 to 50 g/10 minutes, from 1 to 30 g/10 minutes,from 6 g/10 minutes or from 0.3 to 10 g/10 minutes. In certainembodiments, the melt index for the ethylene/α-olefin polymers is 1 g/10minutes, 5 g/10 minutes 10 g/10, 15 g/10 minutes, 20 g/10 min or 24 g/10min.

The polymers can have molecular weights, M_(w), from 1,000 g/mole to5,000,000 g/mole, preferably from 1000 g/mole to 1,000,000, morepreferably from 10,000 g/mole to 500,000 g/mole, and especially from10,000 g/mole to 300,000 g/mole. The density of the inventive polymerscan be from 0.80 to 0.99 g/cm³ and preferably for ethylene containingpolymers from 0.85 g/cm³ to 0.97 g/cm³. In certain embodiments, thedensity of the ethylene/α-olefin polymers ranges from 0.860 to 0.925g/cm³ or 0.867 to 0.910 g/cm³. In certain embodiments, the density ofthe ethylene/α-olefin polymers is from about 0.860 to 0.900 g/cm³,preferably from about 0.860 to 0.885 g/cm³, more preferably from about0.860 to 0.883 g/cm³, and most preferably from about 0.863 to 0.880g/cm³.

The process of making the polymers has been disclosed in the followingpatent applications: U.S. Provisional Application No. 60/553,906, filedMar. 17, 2004; U.S. Provisional Application No. 60/662,937, filed Mar.17, 2005; U.S. Provisional Application No. 60/662,939, filed Mar. 17,2005; U.S. Provisional Application No. 60/5662938, filed Mar. 17, 2005;PCT Application No. PCT/US2005/008916, filed Mar. 17, 2005; PCTApplication No. PCT/US2005/008915, filed Mar. 17, 2005; and PCTApplication No. PCT/US2005/008917, filed Mar. 17, 2005, all of which areincorporated by reference herein in their entirety. For example, onesuch method comprises contacting ethylene and optionally one or moreaddition polymerizable monomers other than ethylene under additionpolymerization conditions with a catalyst composition comprising:

the admixture or reaction product resulting from combining:

(A) a first olefin polymerization catalyst having a high comonomerincorporation index,

(B) a second olefin polymerization catalyst having a comonomerincorporation index less than 90 percent, preferably less than 50percent, most preferably less than 5 percent of the comonomerincorporation index of catalyst (A), and

(C) a chain shuttling agent.

Representative catalysts and chain shuttling agent are as follows.

Catalyst (A1) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740.

Catalyst (A2) is[N-(2,6-di(1-methylethyl)phenyl)amido)(2-methylphenyl)(1,2-phenylene-(6-pyridin-2-diyl)methane)]hafniumdimethyl, prepared according to the teachings of WO 03/40195,2003US0204017, U.S. Ser. No. 10/429,024, filed May 2, 2003, and WO04/24740.

Catalyst (A3) isbis[N,N′″-(2,4,6-tri(methylphenyl)amido)ethylenediamine]hafniumdibenzyl.

Catalyst (A4) isbis((2-oxoyl-3-(dibenzo-1H-pyrrole-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)cyclohexane-1,2-diylzirconium (IV) dibenzyl, prepared substantially according to theteachings of US-A-2004/0010103.

Catalyst (B1) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconium dibenzyl

Catalyst (B2) is1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(2-methylcyclohexyl)-immino)methyl)(2-oxoyl)zirconium dibenzyl

Catalyst (C1) is(t-butylamido)dimethyl(3-N-pyrrolyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the techniques of U.S. Pat.No. 6,268,444:

Catalyst (C2) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,7a-η-inden-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings ofUS-A-2003/004286:

Catalyst (C3) is(t-butylamido)di(4-methylphenyl)(2-methyl-1,2,3,3a,8a-η-s-indacen-1-yl)silanetitaniumdimethyl prepared substantially according to the teachings ofUS-A-2003/004286:

Catalyst (D1) is bis(dimethyldisiloxane)(indene-1-yl)zirconiumdichloride available from Sigma-Aldrich:

Shuttling Agents The shuttling agents employed include diethylzinc,di(i-butyl)zinc, di(n-hexyl)zinc, triethylaluminum, trioctylaluminum,triethylgallium, i-butylaluminum bis(dimethyl(t-butyl)siloxane),i-butylaluminum bis(di(trimethylsilyl)amide), n-octylaluminumdi(pyridine-2-methoxide), bis(n-octadecyl)i-butylaluminum,i-butylaluminum bis(di(n-pentyl)amide), n-octylaluminumbis(2,6-di-t-butylphenoxide, n-octylaluminum di(ethyl(1-naphthyl)amide),ethylaluminum bis(t-butyldimethylsiloxie), ethylaluninumdi(bis(trimethylsilyl)amide), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide), n-octylaluminumbis(dimethyl(t-butyl)siloxide, ethylzinc (2,6-diphenylphenoxide), andethylzinc (t-butoxide).

Preferably, the foregoing process takes the form of a continuoussolution process for forming block copolymers, especially multi-blockcopolymers, preferably linear multi-block copolymers of two or moremonomers, more especially ethylene and a C₃₋₂₀ olefin or cycloolefin,and most especially ethylene and a C₄₋₂₀ α-olefin, using multiplecatalysts that are incapable of interconversion. That is, the catalystsare chemically distinct. Under continuous solution polymerizationconditions, the process is ideally suited for polymerization of mixturesof monomers at high monomer conversions. Under these polymerizationconditions, shuttling from the chain shuttling agent to the catalystbecomes advantaged compared to chain growth, and multi-block copolymers,especially linear multi-block copolymers are formed in high efficiency.

The inventive interpolymers may be differentiated from conventional,random copolymers, physical blends of polymers, and block copolymersprepared via sequential monomer addition, fluxional catalysts, anionicor cationic living polymerization techniques. In particular, compared toa random copolymer of the same monomers and monomer content atequivalent crystallinity or modulus, the inventive interpolymers havebetter (higher) heat resistance as measured by melting point, higher TMApenetration temperature, higher high-temperature tensile strength,and/or higher high-temperature torsion storage modulus as determined bydynamic mechanical analysis. Compared to a random copolymer containingthe same monomers and monomer content, the inventive interpolymers havelower compression set, particularly at elevated temperatures, lowerstress relaxation, higher creep resistance, higher tear strength, higherblocking resistance, faster setup due to higher crystallization(solidification) temperature, higher recovery (particularly at elevatedtemperatures), better abrasion resistance, higher retractive force, andbetter oil and filler acceptance.

The inventive interpolymers also exhibit a unique crystallization andbranching distribution relationship. That is, the inventiveinterpolymers have a relatively large difference between the tallestpeak temperature measured using CRYSTAF and DSC as a function of heat offusion, especially as compared to random copolymers containing the samemonomers and monomer level or physical blends of polymers, such as ablend of a high density polymer and a lower density copolymer, atequivalent overall density. It is believed that this unique feature ofthe inventive interpolymers is due to the unique distribution of thecomonomer in blocks within the polymer backbone. In particular, theinventive interpolymers may comprise alternating blocks of differingcomonomer content (including homopolymer blocks). The inventiveinterpolymers may also comprise a distribution in number and/or blocksize of polymer blocks of differing density or comonomer content, whichis a Schultz-Flory type of distribution. In addition, the inventiveinterpolymers also have a unique peak melting point and crystallizationtemperature profile that is substantially independent of polymerdensity, modulus, and morphology. In a preferred embodiment, themicrocrystalline order of the polymers demonstrates characteristicspherulites and lamellae that are distinguishable from random or blockcopolymers, even at PDI values that are less than 1.7, or even less than1.5, down to less than 1.3.

Furthermore, by combining ethylene α-olefins with styrenic blockcopolymers, disadvantages associated with using styrenic block copolymerformulations may be mitigated. For example, thermal instability isassociated with certain styrenic block copolymers. One example isstyrene-isoprene-styrene (SIS). If processed at excessively hightemperatures, SIS is known to undergo chain scission. This can result insignificant decreases in viscosity and loss of mechanical properties.Another example is styrene-butadiene-styrene (SBS). If processed atexcessively high temperatures, SBS is known to undergo cross-linking.This can result in significant increases in viscosity and gel formation.As a result, limitations such as these can result in disadvantagedperformance. Formulation with ethylene α-olefins can mitigate thesedisadvantages.

Moreover, the inventive interpolymers may be prepared using techniquesto influence the degree or level of blockiness. That is, the amount ofcomonomer and length of each polymer block or segment can be altered bycontrolling the ratio and type of catalysts and shuttling agent as wellas the temperature of the polymerization, and other polymerizationvariables. A surprising benefit of this phenomenon is the discovery thatas the degree of blockiness is increased, the optical properties, tearstrength, and high temperature recovery properties of the resultingpolymer are improved. In particular, haze decreases while clarity, tearstrength, and high temperature recovery properties increase as theaverage number of blocks in the polymer increases. By selectingshuttling agents and catalyst combinations having the desired chaintransferring ability (high rates of shuttling with low levels of chaintermination) other forms of polymer termination are effectivelysuppressed. Accordingly, little if any 1-hydride elimination is observedin the polymerization of ethylene/α-olefin comonomer mixtures accordingto embodiments of the invention, and the resulting crystalline blocksare highly, or substantially completely, linear, possessing little or nolong chain branching.

Polymers with highly crystalline chain ends can be selectively preparedin accordance with embodiments of the invention. In elastomerapplications, reducing the relative quantity of polymer that terminateswith an amorphous block reduces the intermolecular dilutive effect oncrystalline regions. This result can be obtained by choosing chainshuttling agents and catalysts having an appropriate response tohydrogen or other chain terminating agents. Specifically, if thecatalyst which produces highly crystalline polymer is more susceptibleto chain termination (such as by use of hydrogen) than the catalystresponsible for producing the less crystalline polymer segment (such asthrough higher comonomer incorporation, regio-error, or atactic polymerformation), then the highly crystalline polymer segments willpreferentially populate the terminal portions of the polymer. Not onlyare the resulting terminated groups crystalline, but upon termination,the highly crystalline polymer forming catalyst site is once againavailable for reinitiation of polymer formation. The initially formedpolymer is therefore another highly crystalline polymer segment.Accordingly, both ends of the resulting multi-block copolymer arepreferentially highly crystalline.

The ethylene α-olefin interpolymers used in the embodiments of theinvention are preferably interpolymers of ethylene with at least oneC₃-C₂₀ α-olefin. Copolymers of ethylene and a C₃-C₂₀ α-olefin areespecially preferred. The interpolymers may further comprise C₄-C₁₈diolefin and/or alkenylbenzene. Suitable unsaturated comonomers usefulfor polymerizing with ethylene include, for example, ethylenicallyunsaturated monomers, conjugated or nonconjugated dienes, polyenes,alkenylbenzenes, etc. Examples of such comonomers include C₃-C₂₀α-olefins such as propylene, isobutylene, 1-butene, 1-hexene, 1-pentene,4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and thelike. 1-Butene and 1-octene are especially preferred. Other suitablemonomers include styrene, halo- or alkyl-substituted styrenes,vinylbenzocyclobutane, 1,4-hexadiene, 1,7-octadiene, and naphthenics(e.g., cyclopentene, cyclohexene and cyclooctene).

While ethylene/α-olefin interpolymers are preferred polymers, otherethylene/olefin polymers may also be used. Olefins as used herein referto a family of unsaturated hydrocarbon-based compounds with at least onecarbon-carbon double bond. Depending on the selection of catalysts, anyolefin may be used in embodiments of the invention. Preferably, suitableolefins are C₃-C₂₀ aliphatic and aromatic compounds containing vinylicunsaturation, as well as cyclic compounds, such as cyclobutene,cyclopentene, dicyclopentadiene, and norbomene, including but notlimited to, norbomene substituted in the 5 and 6 position with C₁-C₂₀hydrocarbyl or cyclohydrocarbyl groups. Also included are mixtures ofsuch olefins as well as mixtures of such olefins with C₄-C₄₀ diolefincompounds.

Examples of olefin monomers include, but are not limited to propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, and 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene,4-methyl-1-pentene, 4,6-dimethyl-1-heptene, 4-vinylcyclohexene,vinylcyclohexane, norbornadiene, ethylidene norbomene, cyclopentene,cyclohexene, dicyclopentadiene, cyclooctene, C₄-C₄₀ dienes, includingbut not limited to 1,3-butadiene, 1,3-pentadiene, 1,4-hexadiene,1,5-hexadiene, 1,7-octadiene, 1,9-decadiene, other C₄-C₄₀ α-olefins, andthe like. In certain embodiments, the α-olefin is propylene, 1-butene,1-pentene, 1-hexene, 1-octene or a combination thereof. Although anyhydrocarbon containing a vinyl group potentially may be used inembodiments of the invention, practical issues such as monomeravailability, cost, and the ability to conveniently remove unreactedmonomer from the resulting polymer may become more problematic as themolecular weight of the monomer becomes too high.

The polymerization processes described herein are well suited for theproduction of olefin polymers comprising monovinylidene aromaticmonomers including styrene, o-methyl styrene, p-methyl styrene,t-butylstyrene, and the like. In particular, interpolymers comprisingethylene and styrene can be prepared by following the teachings herein.Optionally, copolymers comprising ethylene, styrene and a C₃-C₂₀ alphaolefin, optionally comprising a C₄-C₂₀ diene, having improved propertiescan be prepared.

Suitable non-conjugated diene monomers can be a straight chain, branchedchain or cyclic hydrocarbon diene having from 6 to 15 carbon atoms.Examples of suitable non-conjugated dienes include, but are not limitedto, straight chain acyclic dienes, such as 1,4-hexadiene, 1,6-octadiene,1,7-octadiene, 1,9-decadiene, branched chain acyclic dienes, such as5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene;3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene anddihydroocinene, single ring alicyclic dienes, such as1,3-cyclopentadiene; 1,4-cyclohexadiene; 1,5-cyclooctadiene and1,5-cyclododecadiene, and multi-ring alicyclic fused and bridged ringdienes, such as tetrahydroindene, methyl tetrahydroindene,dicyclopentadiene, bicyclo-(2,2,1)-hepta-2,5-diene; alkenyl, alkylidene,cycloalkenyl and cycloalkylidene norbomenes, such as5-methylene-2-norbornene (MNB); 5-propenyl-2-norbomene,5-isopropylidene-2-norbomene, 5-(4-cyclopentenyl)-2-norbornene,5-cyclohexylidene-2-norbomene, 5-vinyl-2-norbomene, and norbornadiene.Of the dienes typically used to prepare EPDMs, the particularlypreferred dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene(ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-2-norbomene (MNB),and dicyclopentadiene (DCPD). The especially preferred dienes are5-ethylidene-2-norbornene (ENB) and 1,4-hexadiene (HD).

One class of desirable polymers that can be made in accordance withembodiments of the invention are elastomeric interpolymers of ethylene,a C₃-C₂₀ α-olefin, especially propylene, and optionally one or morediene monomers. Preferred α-olefins for use in this embodiment of thepresent invention are designated by the formula CH₂=CHR*, where R* is alinear or branched alkyl group of from 1 to 12 carbon atoms. Examples ofsuitable α-olefins include, but are not limited to, propylene,isobutylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and1-octene. A particularly preferred α-olefm is propylene. The propylenebased polymers are generally referred to in the art as EP or EPDMpolymers. Suitable dienes for use in preparing such polymers, especiallymulti-block EPDM type polymers include conjugated or non-conjugated,straight or branched chain-, cyclic- or polycyclic-dienes comprisingfrom 4 to 20 carbons. Preferred dienes include 1,4-pentadiene,1,4-hexadiene, 5-ethylidene-2-norbornene, dicyclopentadiene,cyclohexadiene, and 5-butylidene-2-norbornene. A particularly preferreddiene is 5-ethylidene-2-norbornene.

Because the diene containing polymers comprise alternating segments orblocks containing greater or lesser quantities of the diene (includingnone) and α-olefin (including none), the total quantity of diene andα-olefin may be reduced without loss of subsequent polymer properties.That is, because the diene and α-olefin monomers are preferentiallyincorporated into one type of block of the polymer rather than uniformlyor randomly throughout the polymer, they are more efficiently utilizedand subsequently the crosslink density of the polymer can be bettercontrolled. Such crosslinkable elastomers and the cured products haveadvantaged properties, including higher tensile strength and betterelastic recovery.

In some embodiments, the inventive interpolymers made with two catalystsincorporating differing quantities of comonomer have a weight ratio ofblocks formed thereby from 95:5 to 5:95. The elastomeric polymersdesirably have an ethylene content of from 20 to 90 percent, a dienecontent of from 0.1 to 10 percent, and an α-olefin content of from 10 to80 percent, based on the total weight of the polymer. Furtherpreferably, the multi-block elastomeric polymers have an ethylenecontent of from 60 to 90 percent, a diene content of from 0.1 to 10percent, and an α-olefin content of from 10 to 40 percent, based on thetotal weight of the polymer. Preferred polymers are high molecularweight polymers, having a weight average molecular weight (Mw) from10,000 to about 2,500,000, preferably from 20,000 to 500,000, morepreferably from 20,000 to 350,000, and a polydispersity less than 3.5,more preferably less than 3.0, and a Mooney viscosity (ML (1+4) 125° C.)from 1 to 250. More preferably, such polymers have an ethylene contentfrom 65 to 75 percent, a diene content from 0 to 6 percent, and anα-olefin content from 20 to 35 percent.

The ethylene/α-olefin interpolymers can be functionalized byincorporating at least one functional group in its polymer structure.Exemplary functional groups may include, for example, ethylenicallyunsaturated mono- and di-functional carboxylic acids, ethylenicallyunsaturated mono- and di-functional carboxylic acid anhydrides, saltsthereof and esters thereof. Such functional groups may be grafted to anethylene/α-olefin interpolymer, or it may be copolymerized with ethyleneand an optional additional comonomer to form an interpolymer ofethylene, the functional comonomer and optionally other comonomer(s).Means for grafting functional groups onto polyethylene are described forexample in U.S. Pat. Nos. 4,762,890, 4,927,888, and 4,950,541, thedisclosures of these patents are incorporated herein by reference intheir entirety. One particularly useful functional group is malicanhydride.

The amount of the functional group present in the functionalinterpolymer can vary. The functional group can typically be present ina copolyrner-type functionalized interpolymer in an amount of at leastabout 1.0 weight percent, preferably at least about 5 weight percent,and more preferably at least about 7 weight percent. The functionalgroup will typically be present in a copolymer-type functionalizedinterpolymer in an amount less than about 40 weight percent, preferablyless than about 30 weight percent, and more preferably less than about25 weight percent.

The amount of the ethylene/α-olefin interpolymer in the polymer blenddisclosed herein can be from about 5 to about 95 wt %, from about 10 toabout 90 wt %, from about 20 to about 80 wt %, from about 30 to about 70wt %, from about 10 to about 50 wt %, from about 50 to about 90 wt %,from about 60 to about 90 wt %, or from about 70 to about 90 wt % of thetotal weight of the polymer blend.

More on Block Index

Random copolymers satisfy the following relationship. See P. J. Flory,Trans. Faraday Soc., 51, 848 (1955), which is incorporated by referenceherein in its entirety. $\begin{matrix}{{\frac{1}{T_{m}} - \frac{1}{T_{m}^{0}}} = {{- ( \frac{R}{\Delta\quad H_{u}} )}\ln\quad P}} & (1)\end{matrix}$

In Equation 1, the mole fraction of crystallizable monomers, P, isrelated to the melting temperature, T_(m), of the copolymer and themelting temperature of the pure crystallizable homopolymer, T_(m) ⁰. Theequation is similar to the relationship for the natural logarithm of themole fraction of ethylene as a function of the reciprocal of the ATREFelution temperature (° K) as shown in FIG. 8 for various homogeneouslybranched copolymers of ethylene and olefins.

As illustrated in FIG. 8, the relationship of ethylene mole fraction toATREF peak elution temperature and DSC melting temperature for varioushomogeneously branched copolymers is analogous to Flory's equation.Similarly, preparative TREF fractions of nearly all random copolymersand random copolymer blends likewise fall on this line, except for smallmolecular weight effects.

According to Flory, if P, the mole fraction of ethylene, is equal to theconditional probability that one ethylene unit will precede or followanother ethylene unit, then the polymer is random. On the other hand ifthe conditional probability that any 2 ethylene units occur sequentiallyis greater than P, then the copolymer is a block copolymer. Theremaining case where the conditional probability is less than P yieldsalternating copolymers.

The mole fraction of ethylene in random copolymers primarily determinesa specific distribution of ethylene segments whose crystallizationbehavior in turn is governed by the minimum equilibrium crystalthickness at a given temperature. Therefore, the copolymer melting andTREF crystallization temperatures of the inventive block copolymers arerelated to the magnitude of the deviation from the random relationshipin FIG. 8, and such deviation is a useful way to quantify how “blocky” agiven TREF fraction is relative to its random equivalent copolymer (orrandom equivalent TREF fraction). The term “blocky” refers to the extenta particular polymer fraction or polymer comprises blocks of polymerizedmonomers or comonomers. There are two random equivalents, onecorresponding to constant temperature and one corresponding to constantmole fraction of ethylene. These form the sides of a right triangle asshown in FIG. 9, which illustrates the definition of the block index.

In FIG. 9, the point (T_(X), P_(X)) represents a preparative TREFfraction, where the ATREF elution temperature, T_(X), and the NMRethylene mole fraction, P_(X), are measured values. The ethylene molefraction of the whole polymer, P_(AB), is also measured by NMR. The“hard segment” elution temperature and mole fraction, (T_(A), P_(A)),can be estimated or else set to that of ethylene homopolymer forethylene copolymers. The T_(AB) value corresponds to the calculatedrandom copolymer equivalent ATREF elution temperature based on themeasured P_(AB). From the measured ATREF elution temperature, T_(X), thecorresponding random ethylene mole fraction, P_(X0), can also becalculated. The square of the block index is defined to be the ratio ofthe area of the (P_(X), T_(X)) triangle and the (T_(A), P_(AB))triangle. Since the right triangles are similar, the ratio of areas isalso the squared ratio of the distances from (T_(A), P_(AB)) and (T_(X),P_(X)) to the random line. In addition, the similarity of the righttriangles means the ratio of the lengths of either of the correspondingsides can be used instead of the areas.${BI} = {{\frac{{1/T_{X}} - {1/T_{XO}}}{{1/T_{A}} - {1/T_{AB}}}\quad{or}\quad{BI}} = \frac{{{Ln}\quad P_{X}} - {{Ln}\quad P_{XO}}}{{{Ln}\quad P_{A}} - {{Ln}\quad P_{AB}}}}$

It should be noted that the most perfect block distribution wouldcorrespond to a whole polymer with a single eluting fraction at thepoint (T_(A), P_(AB)), because such a polymer would preserve theethylene segment distribution in the “hard segment”, yet contain all theavailable octene (presumably in runs that are nearly identical to thoseproduced by the soft segment catalyst). In most cases, the “softsegment” will not crystallize in the ATREF (or preparative TREF).

The Compositions of the Present Invention

The compositions of matter of the present invention comprise theethylene/α-olefin interpolymer described previously and a styrenic blockcopolymer. While any density ethylene/α-olefin interpolymer may beuseful, in general, the lower the density, the more elastic the polymerwill be. It is particularly preferred that the density of theinterpolymer be from about 0.85 to 0.900 g/cm³, preferably from about0.855 to 0.885 g/cm³, more preferably from about 0.860 to 0.883 g/cm³,and most preferably from about 0.863 to 0.880 g/cm³.

The Styrenic Block Copolymer

Examples of styrenic block copolymers suitable for the invention aredescribed in but is not limited to EP0712892 B1; WO204041538 A1; U.S.Pat. No. 6,582,829 B1; US 2004/0087235 A1; US 2004/0122408 A1; US2004/0122409 A1; U.S. Pat. No. 4,789,699; U.S. Pat. No. 5,093,422; U.S.Pat. No. 5,332,613; U.S. Pat. No. 6,916,750 B2; US 2002/0052585 A1; U.S.Pat. No. 6,323,389 B1; and U.S. Pat. No. 5,169,706, which areincorporated by reference for their teachings regarding styrenic blockcopolymers.

In general, styrenic block copolymers suitable for the invention have atleast two monoalkenyl arene blocks, preferably two polystyrene blocks,separated by a block of saturated conjugated diene comprising less than20% residual ethylenic unsaturation, prefererably a saturatedpolybutadiene block. The preferred styrenic block copolymers have alinear structure although branched or radial polymers or functionalizedblock copolymers make useful compounds.

Typically, polystyrene-saturated polybutadiene-polystyrene (S-EB-S) (Sis styrene, E is ethylene, and B is butylene) and polystyrene-saturatedpolyisoprene-polystyrene (S-EP-S) (P is propylene) block copolymerscomprise polystyrene endblocks having a number average molecular weightfrom 5,000 to 35,000 and saturated polybutadiene or saturatedpolyisoprene midblocks having a number average molecular weight from20,000 to 170,000. The saturated polybutadiene blocks preferably havefrom 35% to 55% 1, 2-configuration and the saturated polyisoprene blockspreferably have greater than 85% 1, 4-configuration.

The total number average molecular weight of the styrenic blockcopolymer is preferably from 30,000 to 250,000 if the copolymer has alinear structure. Such block copolymers typically have an averagepolystyrene content from 10% by weight to 35% by weight.

A S-EB-S block copolymer useful in a particularly preferred aspect ofthe present invention is available from KRATON Polymers LLC (Houston,Tex.) and has a number average molecular weight of 50,000 grams per molewith polystyrene endblocks each having a number average molecular weightof 7,200 grams per mole and polystyrene content of 30% by weight.

Styrenic block copolymers may be prepared by methods known to one ofordinary skill in the art. For example, the styrenic block copolymersmay be manufactured using free-radical, cationic and anionic initiatorsor polymerization catalysts. Such polymers may be prepared using bulk,solution or emulsion techniques. In any case, the styrenic blockcopolymer contains ethylenic unsaturation at a minimum, and generally,will be recovered as a solid such as a crumb, a powder, a pellet, or thelike.

In general, when solution anionic techniques are used, conjugateddiolefin polymers and copolymers of conjugated diolefins and alkenylaromatic hydrocarbons are prepared by contacting the monomer or monomersto be polymerized simultaneously or sequentially with an organoalkalimetal compound in a suitable solvent at a temperature in the range offrom 150° C. to 300° C., preferably at a temperature in the range offrom 0° C. to 100° C. Particularly effective anionic polymerizationinitiators are organolithium compounds having the general formula:RLi_(n) wherein R is an aliphatic, cycloaliphatic, aromatic, oralkyl-substituted aromatic hydrocarbon radical having from 1 to 20carbon atoms; and n is an integer of 1 to 4.

In addition to sequential techniques to obtain triblocks, tetrablocks,and higher orders of repeating structures, anionic initiators, at aminimum, can be used to prepare diblocks of styrene- polydiene having areactive (“live”) chain end on the diene block which can be reactedthrough a coupling agent to create, for example, (S—I)_(x)Y or(S—B)_(x)Y structures wherein x is an integer from 2 to 30, Y is acoupling agent, I is isoprene, B is butadiene and greater than 65percent of S—I or S—B diblocks are chemically attached to the couplingagent. Y usually has a molecular weight which is low compared to thepolymers being prepared and can be any of a number of materials known inthe art, including halogenated organic compounds; halogenated alkylsilanes; alkoxy silanes; various esters such as alkyl and arylbenzoates, difunctional aliphatic esters such as dialkyl adipates andthe like; polyfunctional agents such as divinyl benzene (DVB) and lowmolecular weight polymers of DVB. Depending on the selected couplingagent, the final polymer can be a fully or partially coupled lineartriblock polymer (x=2), i.e., SIYIS; or in a branched, radial or starconfiguration. The coupling agent, being of low molecular weight, doesnot materially affect the properties of the final polymer. DVB oligomeris commonly used to create star polymers, wherein the number of dienearms can be 7 to 20 or even higher.

It is not required in coupled polymers that the diblock units all beidentical. In fact, diverse “living” diblock units can be broughttogether during the coupling reaction giving a variety of unsymmetricalstructures, i.e., the total diblock chain lengths can be different, aswell as the sequential block lengths of styrene and diene.

Preferably, the styrenic block copolymers are hydrogenated to improveweatherability and oxidation stability. In general, the hydrogenation orselective hydrogenation of the polymer may be accomplished using any ofthe several hydrogenation processes known in the prior art. For example,the hydrogenation may be accomplished using methods such as thosetaught, in U.S. Pat. Nos. 3,494,942; 3,634,594; 3,670,054; 3,700,633;and 27,145, which are incorporated by reference for their teachingregarding hydrogenation of styrenic block copolymers and the polymersthat result therefrom. The methods known in the prior art forhydrogenating polymers containing ethylenic unsaturation and forhydrogenating or selectively hydrogenating polymers containing aromaticand ethylenic unsaturation, involve the use of a suitable catalyst,particularly a catalyst or catalyst precursor comprising an iron groupmetal atom, particularly nickel or cobalt, and a suitable reducing agentsuch as an aluminum alkyl.

In general, the hydrogenation will be accomplished in a suitable solventat a temperature in the range of from 20° C. to 100° C. and at ahydrogen partial pressure in the range of from 7 atm (10⁵ Pa) to 340 atm(10⁵ Pa), preferably 7 atm (10⁵ Pa) to 70 atm (10⁵ Pa). Catalystconcentrations are generally in the range of from 10 ppm (wt) to 500 ppm(wt) of iron group metal based on total solution. Contacting athydrogenation conditions is generally continued for a period of time inthe range of from 60 to 240 minutes. After the hydrogenation iscompleted, the hydrogenation catalyst and catalyst residue will,generally, be separated from the polymer.

Not wishing to be limited by theory, it is thought that thecompatibility of the saturated conjugated diene with the interpolymercontributes to the ability of the composition of the present inventionto exhibit the novel properties present. This is consistent with otherembodiments of the present invention. For example, in a particularembodiment of the present invention, a composition comprises aninterpolymer, SIS, and a minor amount of SEBS which is thought tocompatiblize the interpolymer and SIS. In another embodiment of thepresent invention, a composition comprises an interpolymer, SBS, and aminor amount of SEBS which is thought to compatiblize the interpolymerand SBS.

The Melt Indices of the Present Invention

The preferred melt index (I₂) of the interpolymer is generally at leastabout 0.5, preferably at least about 0.75 g/10 min. Correspondingly, thepreferred melt index (I₂) of the interpolymer is generally less thanabout 30 g/l 0 min., sometimes preferably less than about 24 g/10 min.However, the preferred melt index may often depend upon the desiredconversion process, e.g. blown film, cast film and extrusion lamination,etc.

Blown Film

For blown film processes, the melt index (I₂) of the interpolymer isgenerally at least about 0.5, preferably at least about 0.75 g/10 min.The melt index (I₂) of the interpolymer is generally at most about 5,preferably at most about 3 g/10 min. In addition, it is often preferablethat the ethylene/α-olefin interpolymer be made with a diethyl zincchain shuttling agent wherein the mole ratio of zinc to ethylene is fromabout 0.03×10⁻³ to about 1.5×10⁻³.

Cast Film and Extrusion Lamination

For cast film and extrusion laminate processes, the melt index (I₂) ofthe interpolymer is generally at least about 0.5, preferably at leastabout 0.75, more preferably at least about 3, even more preferably atleast about 4 g/10 min. The melt index (I₂) of the interpolymer isgenerally at most about 20, preferably at most about 17, more preferablyat most about 12, even more preferably at most about 5 g/10 min.

In addition, it is often preferable that the ethylene/α-olefininterpolymer be made with a diethyl zinc chain shuttling agent whereinthe ratio of zinc to ethylene is from about 0.03×10⁻³ to about 1.5×10⁻³.

The composition may contain additional components such as otherpolyolefin based plastomers and/or elastomers. Polyolefin basedelastomers and plastomers/polymers include copolymers of ethylene withat least one other alpha olefin (C₃-C₂₂), as well as copolymers ofpropylene with at least one other alpha olefin (C₂, C₄-C₂₂). In aparticularly preferred embodiment, a second component comprising highpressure low density type resin is employed. Possible materials for useas an additional component include LDPE (homopolymer); ethylenecopolymerized with one or more α-olefin e.g. propylene or butene; andethylene copolymerized with at least one α,β-ethylenically unsaturatedcomonomer, e.g., acrylic acid, methacrylic acid, methyl acrylate andvinyl acetate; branched polypropylene and blends thereof. A suitabletechnique for preparing useful high pressure ethylene copolymercompositions is described in U.S. Pat. No. 4,599,392, the disclosure ofwhich is incorporated herein by reference.

In yet another embodiment of this invention, a third polymer componentmay be used to improve compatibility, miscibility, dispersion, or othercharacteristics among the polymer components as is generally known inthe art.

For additional attributes, any of the polymer components may befunctionalized or modified at any stage. Examples include but are notlimited to grafting, crosslinking, or other methods offunctionalization.

Film layers comprising the composition of the present invention areoften capable of stress relaxation of at most about 60, preferably atmost about 40, more preferably at most about 28% at 75% strain at 100°F. for at least 10 hours.

Meltblown Fiber

Meltblown fibers are fibers formed by extruding a molten thermoplasticmaterial through a plurality of fine, usually circular, capillaries of ameltblowing die as molten threads or filaments into converginghigh-velocity, usually hot, gas (e.g., air) streams which are flowing inthe same direction as the extruded filaments or threads of the moltenthermoplastic material so that the extruded filaments or threads areattenuated, i.e., drawn or extended, to reduce their diameter.

The threads or filaments may be attenuated to microfiber diameter whichmeans the threads or filaments have an average diameter not greater thanabout 75 microns, generally from about 0.5 microns to about 50 microns,and more particularly from about 2 microns to about 40 microns.Thereafter, the meltblown fibers are carried by the high-velocity gasstream and are deposited on a collecting surface to form a web ofrandomly disbursed meltblown fibers. The meltblown process is well-knownand is described in various patents and publications, including NRLReport 4364, “Manufacture of super-Fine Organic Fibers” by B. A. Wendt,E. L. Boone and D. D Fluharty; NRL Report: 5265, “An Improved Device forthe Formation of Super-Fine Thermoplastic Fibers” by K. D Lawrence, R.T. Lukas and J. A. Young; U.S. Pat. No.3,676,242 to Prentice; and U.S.Pat. No. 3,849,241 to Buntin et al. The foregoing references areincorporated herein in by reference in their entirety. Meltblown fibersare microfibers which may be continuous or discontinuous, are generallysmaller than 10 microns in average diameter and are generally tacky whendeposited onto a collecting surface.

Preparation of Blends

Blends can be prepared by any suitable means known in the art includingtumble dry-blending, weigh-feeding, solvent blending, melt blending viacompound or side-arm extrusion, or the like as well as combinationsthereof.

The components of the blends of the current invention can be used in achemically and/or physically modified form to prepare the inventivecomposition. Such modifications can be accomplished by any knowntechnique such as, for example, by ionomerization and extrusiongrafting.

Additives such as antioxidants (e.g., hindered phenolics such asIrganox® o 1010 or Irganox® 1076 supplied by Ciba Geigy), phosphites(e.g., Irgafos® 168 also supplied by Ciba Geigy), cling additives (e.g.,PIB), Standostab PEPQ™ (supplied by Sandoz), pigments, colorants,fillers, and the like can also be included in the ethylene polymerextrusion composition of the present invention. The article made from orusing the inventive composition may also contain additives to enhanceantiblocking and coefficient of friction characteristics including, butnot limited to, untreated and treated silicon dioxide, talc, calciumcarbonate, and clay, as well as primary, secondary and substituted fattyacid amides, chill roll release agents, silicone coatings, etc. Otheradditives may also be added to enhance the anti-fogging characteristicsof, for example, transparent cast films, as described, for example, inU.S. Pat. No. 4,486,552, the disclosure of which is incorporated hereinby reference. Still other additives, such as quaternary ammoniumcompounds alone or in combination with ethylene-acrylic acid (EAA)copolymers or other functional polymers, may also be added to enhancethe antistatic characteristics of coatings, profiles and films of thisinvention and allow, for example, the packaging or making ofelectronically sensitive goods. Other functional polymers such as maleicanhydride grafted polyethylene may also be added to enhance adhesion,especially to polar substrates.

Alternatively, the polymeric and non-polymeric components may becombined with steps that include solution blending (also known assolvent blending) or a combination of melt and solution methods.Solution blending methods include but are not limited to multiplereactors in series, parallel, or combinations thereof. As solutionmethods can sometimes result in better dispersion of the components,greater efficacy of the second component is anticipated. Benefits mayinclude using less second component with maintenance of greater elasticproperties such as reduced set strain and less hysteresis.

Monolayer or multilayer elastic films and laminates comprising theinventive composition can be prepared by any means including blown filmtechniques, coextrusion, laminations and the like and combinationsthereof, including those techniques described below. When the inventivecomposition is used in multilayered constructions, substrates oradjacent material layers can be polar or nonpolar including for example,but not limited to, paper products, metals, ceramics, glass and variouspolymers, particularly other polyolefins, and combinations thereof. If apolymer substrate is used, it may take a variety of forms including butnot limited to webs, foams, fabrics, nonwovens, films etc. Particularlypreferred laminates often comprise a nonwoven fabric selected from thegroup consisting of melt blown, spunbond, carded staple fibers,spunlaced staple fibers, and air laid staple fibers. The fabric maycomprise two or more compositionally different fibers. For example, thefabric may comprise a multi-component polymeric fiber, wherein at leastone of the polymeric components comprises at least a portion of thefiber's surface. These nonwovens and the fibers that comprise them canbe bonded in a variety of methods known to those of ordinary skill inthe art. These methods include but are not limited to calendaring,ultrasonic welding, chemical binders, adhesives, high energy electronbeams, and/or lasers etc.

Fabricated articles comprising the inventive compositions may beselected from the group consisting of adult incontinence articles,feminine hygiene articles, infant care articles, surgical gowns, medicaldrapes, household cleaning articles, expandable food covers, andpersonal care articles.

Examples of processes, manufacture, and articles that may benefit fromemploying the inventive composition and may be suitable for use with thecurrent inventions include, but are not limited to, EP0575509B1,EP0575509B1, EP0707106B1, EP0707106B 1, EP472942B1, EP472942B1, U.S.Pat. No. 3,833,973, U.S. Pat. No. 3,860,003, U.S. Pat. No. 4,116,892,U.S. Pat. No. 4,422,892, U.S. Pat. No. 4,525,407, U.S. Pat. No.4,573,986, U.S. Pat. No. 4,636,207, U.S. Pat. No. 4,662,875, U.S. Pat.No. 4,695,278, U.S. Pat. No. 4,704,116, U.S. Pat. No. 4,713,069, U.S.Pat. No. 4,720,415, U.S. Pat. No. 4,795,454, U.S. Pat. No. 4,798,603,U.S. Pat. No. 4,808,178, U.S. Pat. No. 4,846,815, U.S. Pat. No.4,888,231, U.S. Pat. No. 4,900,317, U.S. Pat. No. 4,909,803, U.S. Pat.No. 4,938,753, U.S. Pat. No. 4,938,757, U.S. Pat. No. 4,940,464, U.S.Pat. No. 4,963,140, U.S. Pat. No. 4,965,122, U.S. Pat. No. 4,981,747,U.S. Pat. No. 5,019,065, U.S. Pat. No. 5,032,122, U.S. Pat. No.5,061,259, U.S. Pat. No. 5,085,654, U.S. Pat. No. 5,114,781, U.S. Pat.No. 5116662, U.S. Pat. No. 5,137,537, U.S. Pat. No. 5,147,343, U.S. Pat.No. 5,149,335, U.S. Pat. No. 5,151,092, U.S. Pat. No. 5,156,793, U.S.Pat No. 5,167,897, U.S. Pat. No. 5,169,706, U.S. Pat. No. 5,226,992,U.S. Pat. No. 5,246,433, U.S. Pat. No. 5,286,543, U.S. Pat. No.5,318,555, U.S. Pat. No. 5336545, U.S. Pat. No. 5,360,420, U.S. Pat. No.5,364,382, U.S. Pat. No. 5,415,644, U.S. Pat. No. 5,429,629, U.S. Pat.No. 5,490,846, U.S. Pat. No. 5492751, U.S. Pat. No. 5,496,298, U.S. Pat.No. 5,509,915, U.S. Pat. No. 5,514,470, U.S. Pat. No. 5,518,801, U.S.Pat. No. 5,522,810, U.S. Pat. No. 5,562,646, U.S. Pat. No. 5,562,650,U.S. Pat. No. 5,569,234, U.S. Pat. No. 5,591,155, U.S. Pat. No.5,599,338, U.S. Pat. No. 5,601,542, U.S. Pat. No. 5643588, U.S. Pat. No.5,650,214, U.S. Pat. No. 5,674,216, U.S. Pat. No. 5,685,874, U.S. Pat.No. 5,691,035, U.S. Pat. No. 5,772,825, U.S. Pat. No. 5779831, U.S. Pat.No. 5,836,932, U.S. Pat. No. 5,837,352, U.S. Pat. No. 5,843,056, U.S.Pat. No. 5,843,057, U.S. Pat. No. 5,858,515, U.S. Pat. No. 5879341, U.S.Pat. No. 5,882,769, U.S. Pat. No. 5,891,544, U.S. Pat. No. 5,916,663,U.S. Pat. No. 5,931,827, U.S. Pat. No. 5,968,025, U.S. Pat. No. 5993433,U.S. Pat. No. 6,027,483, U.S. Pat. No. 6,075,179, U.S. Pat. No.6,107,537, U.S. Pat. No. 6,118,041, U.S. Pat. No. 6,153,209, U.S. Pat.No. 6297424, U.S. Pat. No. 6,307,119, U.S. Pat. No. 6,318,555, U.S. Pat.No. 6,428,526, U.S. Pat. No. 6,491,165, U.S. Pat. No. 6,605,172, U.S.Pat. No. 6627786, U.S. Pat. No. 6,635,797, U.S. Pat. No. 6,642,427, U.S.Pat. No. 6,645,190, U.S. Pat. No. 6,689,932, U.S Pat. No. 6,763,944,U.S. Pat. No. 6,849,067, WO9003258A1, WO9003464A2, U.S. Pat. No.4,116,892 and U.S. Pat. No. 5,1567,93.

The composition of the present invention may be used in a method ofproducing a composite elastic material comprising at least onegatherable web bonded to at least one elastic web, such as disclosed inU.S. Pat. No. 4,720,415, which is herein incorporated by reference inits entirety. Such method comprises (a) tensioning an elastic web (whichmay comprise a fibrous web such as a nonwoven web of elastomeric fibers,e.g., meltblown elastomeric fibers) to elongate it; (b) bonding theelongated elastic web to at least one gatherable web under conditionswhich soften at least portions of the elastic web to form a bondedcomposite web; and (c) relaxing the composite web immediately after thebonding step whereby the gatherable web is gathered to form thecomposite elastic material. The composition of the present invention maybe an elastic web or a gatherable web. Other aspects of the methodprovide for maintaining the fibrous elastic web in a stretched conditionduring bonding, at an elongation of at least about 25 percent,preferably about 25 percent to over 500 percent, for example, about 25percent to 550 percent elongation during the bonding.

The method may also include bonding the elongated elastic web to thegatherable web by overlaying the elastic and gatherable webs andapplying heat and pressure to the overlaid webs, for example, by heatingbonding sites on the elastic web to a temperature of from at least about65 ° C. to about 120 ° C., preferably from at least about 70° C. toabout 90 ° C.

In accordance with the present invention there is also provided anelastic composite material comprising an elastic web bonded to at leastone gatherable web which is extensible and contractible with the elasticweb upon stretching and relaxing of the composite material, the elasticcomposite material being made by a method as described above, whereinthe elastic composite material comprises the composition of the presentinvention.

In accordance with another aspect of the present invention, the elasticweb is bonded to the gatherable web at a plurality of spaced-apartlocations in a repeating pattern and the gatherable web is gatheredbetween the bonded locations.

Other aspects of the invention provide that the elastic web may comprisea nonwoven web of elastomeric fibers, preferably elastomericmicrofibers, such as, for example, an elastomeric nonwoven web ofmeltblown elastomeric fibers or an elastomeric film.

Other aspects of the invention include one or more of the following inany combination: the elastic web, e.g., a fibrous elastic web, is bondedto the gatherable web at a plurality of spaced-apart locations in arepeating pattern and the gatherable web is gathered between the bondedlocations; the elastic web preferably has a low basis weight of fromabout 5 to about 300, preferably from about 5 to about 200, grams persquare meter gm/m²), for example, from about 5 to about 100 grams persquare meter, although its basis weight can be much higher; and, thegatherable web is a nonwoven, non-elastic material, preferably onecomposed of fibers formed from materials selected from the groupincluding polyester fibers, e.g., poly(ethylene terephthalate) fibers,polyolefin fibers, polyamide fibers, e.g., nylon fibers, cellulosicfibers, e.g., cotton fibers, and mixtures thereof. A particular aspectof the present invention is to use elastic and/or lower modulusnonwovens including those comprising propylene copolymers. Such fiberscan comprise copolymers of propylene and ethylene. Suitable resins forfabricating such fibers including but are not limited to VERSIFY™(available from The Dow Chemical Company) and VISTAMAXX™ (available fromExxonMobil Corporation). In another aspect of the present invention, thepolyolefin fibers comprise olefin block copolymers such as thosegenerally described in the present application as well as inWO2005/090427 and US 2006-0199930 A1 . Not wishing to be bound bytheory, it is thought that a nonwoven comprising lower modulus and/orextensible and/or elastic fibers can enable greater compliance andelasticity to the overall structure. In another embodiment, thestructure comprises a nonwoven which comprises a mixture of anycombination two or more fiber types from the possible group ofconventional, lower modulus, extensible, and elastic fibers.Alternatively, the gatherable web may be any suitable woven fabric. Thefibers of any of the above embodiments may be made in a number of formsknown to those of ordinary skill in the art. These forms include but arenot limited to monofilament, bicomponent, multicomponent, side-by-side,coaxial, islands-in-the-sea etc.

The compositions of the present invention may also be used in a methodof producing a composite elastic necked-bonded material including one ormore layers of necked material joined to one or more layers of elasticsheet, as disclosed in U.S. Pat. Nos. 5,226,992 and 5,336,545, which areherein incorporated by reference in their entirety. The method comprisesapplying a tensioning force to at least one neckable material to neckthe material; and joining the tensioned, necked material to at least oneelastic sheet at least at two locations. The composition of the presentinvention may be used in a neckable material, an elastic sheet or both.The necked bonded material may comprise a laminate comprising thecomposition of the present invention. The necked bonded material mayalso be apertured.

The necked material used as a component of the composite elasticnecked-bonded material is formed from a neckable material. If thematerial is stretchable, it may be necked by stretching in a directiongenerally perpendicular to the desired direction of neck-down. Theneckable material may be any material that can be necked and joined toan elastic sheet. Such neckable materials include knitted and looselywoven fabrics, bonded carded webs, spunbonded webs or meltblown webs.The meltblown web may include meltblown microfibers. The neckablematerial may also have multiple layers such as, for example, multiplespunbonded layers and/or multiple meltblown layers. The neckablematerial may be made of polymers such as, for example, polyolefins.Exemplary polyolefins include polypropylene, polyethylene, ethylenecopolymers and propylene copolymers. In particular, the polyolefin maycomprise olefin block copolymers such as those generally described inthe present application as well as in WO2005/090427 and US 2006-0199930A1 .

The composition of the present invention may also be used in a laminatein a stretched bonded material, a machine direction activated material,a cross direction activated material and a machine and cross directionactivated material.

The elastic sheet may be a pressure sensitive elastomer adhesive sheet.If the elastic sheet is a nonwoven web of elastic fibers or pressuresensitive elastomer adhesive fibers, the fibers may be meltblown fibers.More particularly, the meltblown fibers may be meltblown microfibers.

The elastic sheet and the reversibly necked material may be joined byoverlaying the materials and applying heat and/or pressure to theoverlaid materials. Alternatively, the layers may be joined by usingother bonding methods and materials such as, for example, adhesives,pressure sensitive adhesives, ultrasonic welding, high energy electronbeams, and/or lasers. In one aspect, the elastic sheet may be formeddirectly on the necked material utilizing processes, such as, forexample, meltblowing processes and film extrusion processes.

Other aspects of this invention provide that the pressure sensitiveelastomer adhesive sheet and necked material may be joined without theapplication of heat such as, for example, by a pressure bonderarrangement or by tensioned wind-up techniques.

When an elastic sheet is formed directly on the necked materialutilizing film extrusion processes, the method of the present inventionmay include the following steps: 1) providing a continuously advancingtensioned, necked material; 2) extruding a film of substantially moltenelastomer through a die tip; 3) depositing the extruded elastomeric filmonto the tensioned, necked material within from about 0.1 to about 1second of exiting the die tip to form a multilayer material; and 4)immediately applying pressure to the multilayer material to bond thetensioned, necked material to the elastomeric film, as is disclosed inU.S. Pat. No. 5,514,470, which is herein incorporated by reference inits entirety.

Generally speaking, the tensioned, necked material may be material thatwas pre-necked and treated to remain in its necked condition (e.g., areversibly necked material) or may be provided by applying a tensioningforce to at least one neckable material to neck the material.

According to the invention, the film of elastomer may be deposited ontothe tensioned, necked material within from about 0.25 seconds to about0.5 seconds of exiting the die tip. For example, the film of elastomeris deposited onto the tensioned, necked material within from about 0.3seconds to about 0.45 seconds of exiting the die tip.

According to one aspect of the invention, the film of elastomer may beextruded at a temperature of from about 180° C. to about 285° C. Forexample, a film of elastomer may be extruded at a temperature of fromabout 195° C. to about 250° C. Desirably, the film of elastomer may beextruded at a temperature from about 200° C. to about 220° C.

Pressure is applied to bond the necked material to the elastomeric film.This pressure may be applied utilizing, for example, a pressure rollarrangement. The pressure roll arrangement may include at least a firstroll and a second roll configured to provide a gap between the rolls.Generally speaking, the gap setting between the first and second rollsof the pressure roll arrangement is large enough so that the forcerequired to extend the resulting composite elastic material on the firstpull is at least about 25 percent less than the force required to extendan identical composite elastic material prepared in an identicalpressure roll arrangement with the pressure rolls in substantial bondingcontact. For example, the method of the present invention may bepracticed with the gap setting between the pressure rollers at about 15mils (about 0.381 mm) to about 125 mils (about 3.175 mm). As a furtherexample, the method of the present invention may be practiced with thegap setting between the pressure rollers at about 30 mils to about 100mils. Desirably, the method of the present invention is be practicedwith the gap setting between the pressure rollers at about 40 mils toabout 65 mils.

Alternatively, and/or additionally, pressure applied to bond the neckedmaterial to the extruded elastomeric film may be generated by thetensioning force on the tensioned, necked material as the elastomericfilm is temporarily configured between a layer of tensioned, neckedmaterial and a roller or surface (e.g., a protruding roller orprotruding surface).

The elastomeric film may be a film of elastomeric pressure sensitiveelastomer adhesive. The elastomeric pressure sensitive elastomeradhesive may be formed from a blend including an elastomeric polymer ofthe present invention and a tackifying resin.

The present invention also encompasses a composite elastic materialproduced by the method described above.

According to one aspect of the present invention, the method ofproducing a composite elastic necked-bonded material including one ormore layers of necked material joined to one or more layers of elasticsheet includes the following steps: 1) providing a first and secondcontinuously advancing sheet, each sheet being composed of at least onetensioned, necked material and each sheet advancing in intersectingrelationship to form a contact zone; 2) extruding a film ofsubstantially molten elastomer through a die tip between the first andsecond continuously advancing sheet of tensioned, necked material sothat the extruded elastomeric film is deposited into the contact zonewithin from about 0.1 to about 1 second of exiting the die tip to form amultilayer material; and 3) immediately applying pressure to themultilayer material to bond each tensioned, necked material to theelastomeric film.

Generally speaking, the first and second continuously advancing sheetsof tensioned, necked material may be material that was pre-necked andtreated to remain in its necked condition (e.g., a reversibly neckedmaterial) or may be provided by applying a tensioning force to at leastone neckable material to neck the material.

According to the invention, the film of elastomer may be deposited ontothe tensioned, necked material within from about 0.25 seconds to about 1second of exiting the die tip. For example, the film of elastomer may bedeposited onto the tensioned, necked material within from about 0.3seconds to about 0.45 seconds of exiting the die tip.

In an aspect of the invention, the film of elastomer may be extruded ata temperature of from about 180° C. to about 285° C. For example, a filmof elastomer may be extruded at a temperature of from about 195° C. toabout 250° C. Desirably, the film of elastomer may be extruded at atemperature from about 200° C. to about 220° C.

Other aspects of this invention provide that the pressure sensitiveelastomer adhesive sheet and necked material may be joined without theapplication of heat such as, for example, by a pressure bonderarrangement or by tensioned wind-up techniques.

The present invention also comprises a continuous feed spun bondedlaminate comprising the composition of the present invention havingimproved elastic properties at body temperature such as those disclosedin WO 1999/017926 and U.S. Pat. No. 6,323,389, which is hereinincorporated by reference in its entirety. In a preferred embodiment,the laminate comprises a layer of filaments formed by a continuousfilament process, to which is bonded a layer of meltblown fibers. Thiscomposite material is then sandwiched between two layers of spunbondfibers after being stretched. The resulting layers are then passedbetween a pair of niprolls and the resulting laminate is then relaxedprior to winding on a 4:1 takeup roll.

The composition of the present invention is preferably used in thefilament layer. The styrenic block copolymer is preferably a triblockpolystyrene-poly(ethylene/propylene)-polystyrene (“SEPS”) copolymer or apolystyrenepoly(ethylene/butylene)-polystyrene (“SEBS”) copolymer, eachhaving a number average molecular weight of about 81,000 g/mol. Theweight percent of styrene is approximately 18% and the weight percent ofethylene/propylene is approximately 82%. Conventional triblock polymeris typically in the 61,000 g/mol range. The molecular weight increase inthe polymer midblock, while holding the molecular weight of the styreneblock constant, increases the entanglement density, polymer chainpersistence length and the relaxation time. The laminate is particularlyuseful as side panel material in training pants because of theresistance to sagging at body temperature.

In addition, the present invention relates to non-tacky, microtextured,multi-layer elastomeric laminates such as described in EP500590 B 1, andU.S. Pat. Nos. 5,501,679 and 5,691,034, which are herein incorporated byreference in their entirety. The laminates of the present invention arecomprised both of an elastomeric polymeric core layer(s), which provideselastomeric properties to the laminate and one or more polymeric skinlayers which are capable of becoming microtextured. This microtexturingincreases the comfort level of the elastomeric material which iscomplemented by a significant lowering of the laminate's coefficient offriction and modulus. In preferred embodiments of the present inventionthe skin layer further can function to permit controlled release orrecovery of the stretched elastomer, modify the modulus of elasticity ofthe elastomeric laminate and/or stabilize the shape of the elastomericlaminate (i.e., by controlling further necking). The laminates can beprepared by coextrusion of the selected polymers or by application ofone or more elastomer layers onto one or more already formed skinlayer(s). Coextrusion is preferred. The novel non-tacky microtexturedlaminate is obtained by stretching the laminate past the elastic limitof the outer skin layers. The laminate then recovers, which can beinstantaneous, over an extended time period, which is skin layercontrollable, or by the application of heat, which is also skin layercontrollable.

Stretching of the laminate can be uniaxial, sequentially biaxial, orsimultaneously biaxial. The method and degree of stretch allowsignificant control over the resulting microtextured surface.

The elastomer comprises compositions of the present invention. Further,preferably, the elastomer of the invention will sustain only smallpermanent set following deformation and relaxation which set ispreferably 20 to 200 percent and more preferably 20 to 100 percent ofthe original length at 500%. The elastomer of the present inventionshould be stretched to a degree that causes relatively consistentpermanent deformation in a relatively inelastic skin layer. This can beas low as 50% elongation. Preferably, the elastomer is capable ofundergoing up to 300 to 1200% elongation at room temperature, and mostpreferably up to 600 to 800% elongation at room temperature.

In a particular aspect, the composition of the present inventioncomprises a layer in a multilayer structure in which at least one skinlayer is used. In a particular aspect, the skin layer can be formed ofany semi-crystalline or amorphous polymer that is less elastic (e.g.higher permanent set) than the core layer(s) and will undergo permanentdeformation at the stretch percentage that the elastomeric laminate willundergo. Therefore, slightly elastic compounds, such as some olefinicelastomers, e.g. ethylene-propylene elastomers, other olefin blockcopolymers, or ethylene-propylene-diene terpolymer elastomers orethylenic copolymers, e.g., ethylene vinyl acetate, can be used as skinlayers, either alone or in blends. However, the skin layer is generallya polyolefin such as polyethylene, polypropylene, polybutylene or apolyethylene-polypropylene copolymer, but may also be wholly or partlypolyamide such as nylon, polyester such as polyethylene terephthalate,polyvinylidene fluoride, polyacrylate such as poly(methylmethacrylate)(only in blends) and the like, and blends thereof. In oneparticular aspect, the skin layer comprises α-olefins. In anotheraspect, the skin layer comprises olefin block copolymers such as thosegenerally described in the present application as well as inWO2005/090427 and US 2006-0199930 A1. The skin layer material can beinfluenced by the type of elastomer selected. If the elastomeric layeris in direct contact with the skin layer the skin layer should havesufficient adhesion to the elastomeric core layer such that it will notreadily delaminate. Skin-to-core contact has been found to follow threemodes: first, full contact between the core and microtextured skin;second, cohesive failure of the core under the microtexture folds; andthird, adhesive failure of the skin to the core under the microtexturefolds with intermittent skin/core contact at the fold valleys. However,where a high modulus elastomeric layer is used with a softer polymerskin layer attachment may be acceptable yet a microtextured surface maynot form.

The skin layer is used in conjunction with an elastomeric layer and caneither be an outer layer or an inner layer (e.g., sandwiched between twoelastomeric layers). Used as either an outer or inner layer the skinlayer will modify the elastic properties of the elastomeric laminate.

Additives useful in the skin layer include, but are not limited to,mineral oil extenders, antistatic agents, pigments, dyes, antiblockingagents, provided in amounts less than about 15%, starch and metal saltsfor degradability and stabilizers such as those described for theelastomeric core layer.

Other layers may be added between the core layer and the outer layers,such as tie layers to improve the bonding of the layers. Tie layers canbe formed of, or compounded with, typical compounds for this useincluding ethylene copolymers, propylene copolymers, propylene-ethylenecopolymers, olefin block copolymers, maleic anhydride modifiedelastomers, ethyl vinyl acetates and olefins, polyacrylic imides, butylacrylates, peroxides such as peroxypolymers, e.g., peroxyolefins,silanes, e.g., epoxysilanes, reactive polystyrenes, chlorinatedpolyethylene, acrylic acid modified polyolefins and ethyl vinyl acetateswith acetate and anhydride functional groups and the like, which canalso be used in blends or as compatiblizers in one or more of the skinor core layers. Tie layers are particularly useful when the bondingforce between the skin and core is low. This is often the case withpolyethylene skin as its low surface tension resists adhesion. However,any added layers must not significantly affect the microstructuring ofthe skin layers.

In particular, the tie layer may comprise olefin block copolymers suchas those generally described in the present application as well as inWO2005/090427 and US 2006-0199930 A1.

One unique feature of this aspect of the invention is the ability tocontrol the shrink recovery mechanism of the laminate depending on theconditions of film formation, the nature of the elastomeric layer, thenature of the skin layer, the manner in which the laminate film isstretched and the relative thicknesses of the elastomeric and skinlayer(s). By controlling these variables, the laminate film can bedesigned to instantaneously recover, recover over time or recover uponheat activation.

The present invention is also directed to laminates such as thosedescribed above wherein the one or more polymeric skin layers arecapable of becoming microtextured at specified areas along the laminatelength, as described in U.S. Pat. No. 5,344,691, which is hereinincorporated by reference. The microtextured areas will correspond tosections of the laminate that have been activated from an inelastic, toan elastomeric form. In preferred embodiments of the present invention,the skin layer can further function to permit controlled recovery of thestretched elastomer, modify the modulus behavior of the elastomericlaminate and/or stabilize the shape of the elastomeric laminate (e.g.,by controlling necking). The novel, non-tacky microtextured laminate isobtained by stretching the laminate past the elastic limit ofpredetermined regions of the skin layers. This is termed selective orpreferential activation. The laminate then recovers in thesepredetermined regions, which can be instantaneous, over an extended timeperiod, which is skin layer controllable, or by the application of heat,which is also skin layer controllable.

This selective or preferential activation is produced by controlling therelative elastic modulus values of selected cross-sectional areas of thelaminate to be less than modulus values of adjacent cross-sectionalareas. The areas controlled to have reduced modulus will preferentiallyyield when subjected to stress. This will result in either preferentialelastization of specified zones or fully elasticized laminates withhigher strain regions, depending on the location of the areas of lowmodulus and the manner of stretch. Alternatively, the laminate could betreated to enhance or concentrate stress in selected regions. This willyield essentially the same results as providing low modulus regions. Byeither construction, the laminate can activate in selected regions atlower stretch ratios than would normally be required to activate theentire laminate.

The modulus can be controlled by providing one or more layers of thelaminate with relatively low and high modulus areas. This can beaccomplished by selectively altering the physical or chemicalcharacteristics of regions of one or more layers or by providing alayer(s) with regions of diverse chemical composition. Regionallyenhanced stress can be induced by physical or chemical treatment of alayer(s) such as by ablation, scoring, corona treatment or the like.

Viscosity reducing polymers and plasticizers can also be blended withthe elastomers such as low molecular weight polyethylene andpolypropylene polymers and copolymers, or tackifying resins such asWingtack™, aliphatic hydrocarbon tackifiers available from GoodyearChemical Company. Tackifiers can also be used to increase theadhesiveness of an elastomeric layer to a skin layer. Examples oftackifiers include aliphatic or aromatic hydrocarbon liquid tackifiers,polyterpene resin tackifiers, and hydrogenated tackifying resins.Aliphatic hydrocarbon resins are preferred.

Additives such as dyes, pigments, antioxidants, antistatic agents,bonding aids, antiblocking agents, slip agents, heat stabilizers,photostabilizers, foaming agents, glass bubbles, starch and metal saltsfor degradability or microfibers can also be used in the elastomericcore layer(s). Suitable antistatic aids include ethoxylated amines orquaternary amines such as those described, for example, in U.S. Pat. No.4,386,125, which also describes suitable antiblocking agents, slipagents and lubricants. Softening agents, tackifiers or lubricants aredescribed, for example, in U.S. Pat. No. 4,813,947 and includecoumarone-indene resins, terpene resins, hydrocarbon resins and thelike. These agents can also function as viscosity reducing aids.Conventional heat stabilizers include organic phosphates, trihydroxybutyrophenone or zinc salts of alkyl dithiocarbonate. Suitableantioxidants include hindered phenolic compounds and amines possiblywith thiodipropionic acid or aromatic phosphates or tertiary butylcresol. See also U.S. Pat. No. 4,476,180 for suitable additives andpercentages.

The composition of the present invention may also be used in non-tacky,microtextured, multi-layer elastomeric laminated tape backings and thetapes made therefrom, such as those described in U.S. Pat. No.5,354,597,which is herein incorporated by reference in its entirety. The laminatetape backings of the present invention are comprised both of anelastomeric polymeric core layer(s), which provides elastomericproperties to the laminate and one or more polymeric skin layers whichare capable of becoming microtextured. This microtexturing gives thetape natural low adhesion backsize properties, increases inkreceptivity, acts as an adhesive primer, and lowers the laminatecoefficient of friction and modulus. In preferred embodiments of thepresent invention the skin layer further can function to permitcontrolled release or recovery of the stretched elastomer, modify themodulus of elasticity of the elastomeric tape and/or stabilize the shapeof the elastomeric tape. The laminate tape backings may be prepared bycoextrusion of the selected polymers or by application of one or moreelastomer layers onto one or more already formed skin layer(s) or viceversa. Coextrusion is preferred. Pressure-sensitive adhesive(hereinafter adhesive) may be applied by any conventional mechanismincluding coextrusion. The novel microtextured laminate tape and/or tapebacking is obtained by stretching the laminate past the elastic limit ofthe skin layers. The laminate then recovers, which can be instantaneous,over an extended time period, which is skin layer controllable, or bythe application of heat, which is also skin layer controllable.Stretching of the laminate tape or backing can be uniaxial, sequentiallybiaxial, or simultaneously biaxial.

A laminate capable of instantaneous shrink is one in which the stretchedelastomeric laminate will recover more than 15% in 1 sec. A laminatecapable of time shrink is one where the 15% recovery point takes placemore than 1 sec., preferably more than 5 sec., most preferably more than20 sec. after stretch, and a laminate capable of heat shrink is whereless than 15% shrink recovery occurs to the laminate in the first 20seconds after stretch. Percent recovery is the percent that the amountof shrinkage is of the stretched length minus the original length. Forheat shrink, there will be an activation temperature which will initiatesignificant heat activated recovery. The activation temperature used forheat shrink will generally be the temperature that will yield 50% of thetotal possible recovery (T_(a-50)) and preferably this temperature isdefined as the temperature which will yield 90% (T_(a-90)) of the totalpossible recovery. Total possible recovery includes the amount ofpreactivation shrinkage.

Generally, where the skin layer of the laminate tape backing isrelatively thin, the laminate will tend to contract or recoverimmediately. When the skin thickness is increased sufficiently thelaminate can become heat shrinkable. This phenomenon can occur even whenthe elastomeric layer is formed from a non-heat shrinkable material.Further, by careful selection of the thicknesses of the elastomericlayer and the skin layer(s), the temperature at which the laminaterecovers by a set amount can be controlled within a set range. This istermed skin controlled recovery where generally by altering thethickness or composition of the skin, one can raise the activationtemperature of an elastomeric core by a significant degree, generallymore than at least 10° F. (5.6° C.) and preferably by 15° F. (8.3° C.)and more. Although any skin thickness which is effective can beemployed, too thick a skin will cause the laminate to remain permanentlyset when stretched. Generally, where a single skin is less than 30% ofthe laminate this will not occur. For most heat or time shrink materialsthe stretched elastomer must be cooled so that the energy releasedduring stretching does not cause immediate heat activated recovery. Finetuning of the shrink recovery mechanism can be accomplished by theamount of stretch. This overall control over the shrink recoverymechanism can be an extremely important advantage, for example, when theunactivated tape is used in a manufacturing process. This controlpermits adjustment of the recovery mechanism of the elastomeric laminatetape to fit the requirements of a manufacturing process rather than theneed to adjust a manufacturing process to fit the shrink recoverymechanism of the elastomer itself.

Skin controlled recovery may also be used to control the slow or timeshrink recovery mechanism, as with the heat shrink mechanism. Thisshrink recovery mechanism occurs as an intermediate between instant andheat shrink recovery. Skin layer and stretch ratio control of recoveryis possible as in the heat shrink mechanism, with the added ability tochange the shrink mechanism in either direction, i.e., to a heat or aninstant shrink elastomeric laminate tape.

A time shrink recovery laminate tape will also exhibit some heat shrinkcharacteristics and vice versa. For example, a time shrink laminate tapecan be prematurely recovered by exposure to heat, e.g., at a time priorto 20 seconds after stretch.

Recovery can also be initiated for most time shrink and some lowactivation temperature heat shrink recovery laminates by mechanicaldeformation or activation. In this case, the laminate tape is scored,folded, wrinkled, or the like to cause localized stress fractures thatcause localized premature folding of the skin, accelerating formation ofthe recovered microtextured laminate. Mechanical activation can beperformed by any suitable method such as by using a textured roll, ascoring wheel, mechanical deformation or the like.

The laminate tape backings of the present invention may be formed by anyconvenient layer forming process such as pressing layers together,coextruding the layers or stepwise extrusion of layers, but coextrusionis a preferred process. Coextrusion per se is known and is described,for example, in U.S. Pat. Nos. 3,557,265 and 3,479,425. Tubularcoextrusion or double bubble extrusion is also possible. The layers aretypically coextruded through a specialized die and/or feedblock thatwill bring the diverse materials into contact while forming thelaminate.

Whether the laminate backing is prepared by coating, lamination,sequential extrusion, coextrusion or a combination thereof, the laminateformed and its layers will preferably have substantially uniformthicknesses across the laminate backing. Preferably the layers arecoextensive across the width and length of the laminate. With such aconstruction the microtexturing is substantially uniform over theelastomeric laminate surface. Laminates prepared in this manner havegenerally uniform elastomeric properties with a minimum of edge effectssuch as curl, modulus change, fraying and the like. Further, when woundas in a roll of tape, this will minimize formation of hard bands,winding problems, roll telescoping or the like.

The laminate backing of the invention has an unlimited range ofpotential widths, the width limited solely by the fabricating machinerywidth limitations. This allows fabrication of microtextured elastomerictapes for a wide variety of potential uses.

After formation, the laminate tape backing can be stretched past theelastic limit of the skin, which deforms. The laminate tape backing thenis recovered instantaneously, with time or by the application of heat,as discussed above. For heat recovery, the temperature of activation isdetermined by the materials used to form the laminate in the firstinstance. For any particular laminate, the activation temperature,either T_(a-50) or T_(a-90), can be adjusted by varying the skin/coreratio of the laminate, adjusting the percent stretch or the overalllaminate thickness. The activation temperature used for a heat shrinklaminate is generally at least 80° F. (26.7° C.), preferably at least90° F. (32.2° C.) most preferably over 100° F. (37.8° C.). Whenheat-activated, the stretched laminates are quenched on a coolingroller, which prevents the heat generated from the elongation fromactivating laminate recovery. The chill roll is below the activationtemperature.

The composition of the present invention may also be used in improvednon-tacky, microtextured, multi-layer elastomeric laminates, such asthose described in U.S. Pat. Nos 5,422,178 and 5,376,430, both of whichare herein incorporated by reference in their entirety. The laminates ofthe present invention are comprised of an elastomeric polymeric corelayer(s), which provides elastomeric properties to the laminate and oneor more polymeric skin layers. Laminates can be prepared by coextrusionof the selected polymers for the skin and core layers or by applicationof one or more elastomer layer(s) onto one or more already formed skinlayer(s). The novel, non-tacky microtextured laminate is obtained bystretching the laminate past the elastic limit of the skin layers and,while the laminate is stretched, selectively deactivating the elasticityof the laminate at predetermined regions. The laminate then recovers, inthe non-deactivated regions, which can be instantaneous, over anextended time period, which is skin layer controllable, or by theapplication of heat, which is also skin layer controllable.

The selectively deactivated areas provide high-strength inelasticregions. The recovered regions can be microtextured or have detachedskin layers.

These laminates may also be used in pressure-sensitive adhesive backedtapes.

In addition, the laminates may be used such as described in U.S. Pat.No. 5,462,708, which is herein incorporated by reference in itsentirety. In particular, the shrink recovery mechanism of the laminate,after stretching and selective deactivation, depends on the conditionsof film formation, the nature of the elastomeric layer(s), the nature ofthe skin layer(s), the manner in which the laminate film is stretchedand the relative thicknesses of the elastomeric and skin layer(s). Bycontrolling these variables, the laminate film can be designed toinstantaneously recover, recover over time or recover upon heatactivation. Generally, the core-to-single skin layer ratio will be atleast 3, preferably, at least 5 and less than about 100 and mostpreferably at least 5 to about 75. The overall laminate thickness willbe at least 1 mil, preferably at least 2 mils, although preferably lessthan 10 mils for cost and performance considerations. At core-to-skinlayer ratios less than 3, the laminate has a tendency to not recoverwhen stretched. A stretched and selectively deactivated laminate capableof instantaneous shrink is one in which the stretched, non-deactivatedareas of the elastomeric laminate will recover more than 15% in 1 sec. Alaminate capable of time shrink is one where the 15% recovery pointtakes place more than 1 sec., preferably more than 5 sec., mostpreferably more than 20 sec. after stretch, and a laminate capable ofheat shrink is where less than 15% shrink recovery occurs to thelaminate in the first 20 seconds after stretch and will remain capableof heat shrink for weeks after it is stretched. Percent recovery is thepercent that the amount of shrinkage is of the stretched length minusthe original length of the activated area. For heat-shrink laminatesthere will be an activation temperature which will initiate significantheat-activated recovery. The activation temperature used for aheat-shrink laminate will generally be the temperature that will yield50% of the total possible recovery (T_(a-50)) and preferably thistemperature is defined as the temperature which will yield 90%(T_(a-90)) of the total possible recovery. Total possible recoveryincludes the amount of preactivation shrinkage.

Also, as described in U.S. Pat. No. 5,468,428, which is hereinincorporated by reference, the selective or preferential activation isproduced by controlling the relative elastic modulus values of selectedcross-sectional areas of the laminate to be less than modulus values ofadjacent cross-sectional areas. The areas controlled to have reducedmodulus will preferentially yield when subjected to stress. This willresult in either preferential elastization of specified zones or fullyelasticized laminates with higher strain regions, depending on thelocation of the areas of low modulus and the manner of stretch.Alternatively, the laminate could be treated to enhance or concentratestress in selected regions. This will yield essentially the same resultsas providing low modulus regions. By either construction, the laminatecan activate in selected regions at lower stretch ratios than wouldnormally be required activate the entire laminate.

The modulus can be controlled by providing one or more layers of thelaminate with relatively low and high modulus areas. This can beaccomplished by selectively altering the physical or chemicalcharacteristics of regions of one or more layers or by providing alayer(s) with regions of diverse chemical composition. Regionallyenhanced stress can be induced by physical or chemical treatment of alayer(s) such as by ablation, scoring, corona treatment or the like.

The composition of the present invention may also be used in improvednon-tacky, nonelastomeric materials capable of becoming elastomeric whenstretched, as described in U.S. Pat. No. 5,429,856. Such materialscomprise at least one elastomeric core and a surrounding nonelastomericmatrix, preferably prepared by coextrusion. The material of the presentinvention may be used in the elastomeric polymeric core region, whichprovides the elastomeric properties to the material and a polymericmatrix, which is capable of becoming microtextured at specified areas.The microtextured areas will correspond to sections of the material thathave been activated from an inelastic to an elastomeric form. Inpreferred embodiments of the present invention, the matrix materialfurther can function to permit controlled recovery of the stretchedelastomer, modify the modulus of elasticity of the elastomeric materialand/or stabilize the shape of the elastomeric material (e.g., bycontrolling further necking). The material is preferably prepared bycoextrusion of the selected matrix and elastomeric polymers. The novel,non-tacky microtextured form of the material is obtained by stretchingthe material past the elastic limit of the matrix polymer inpredetermined elastic containing regions. The laminate then recovers inthese predetermined regions, which can be instantaneous, over anextended time period, which is matrix material controllable, or by theapplication of heat, which is also matrix material controllable.

In certain constructions, complex periodic macrostructures can formbetween selectively elasticized regions depending on the method anddirection of stretch activation. This can result in elastics with aconsiderable degree of bulk formed with relatively small amounts ofelastic. This is desirable for many applications, particularly ingarments.

Another use for the compositions of the present invention is in filmlaminates as described in U.S. Pat. No. 5,620,780, which is hereinincorporated by reference in its entirety. In particular, thecomposition may be used in a film laminate as an elasticized diaperfastening tab as per, e.g., U.S. Pat. No. 3,800,796. The one or moreelastomeric core(s) could be placed at the desired location whileproviding nonelastic end portions. The elasticized film is preferably 10mm to 50 mm wide for most conventional tape tab constructions. Thisprovides adequate tension without having to stretch the tape too faronto the diaper front. This tab could be cut from film stock containingone or more elastomeric bands. Adhesive or a mechanical fastener (e.g.,hook or loop) element could then be applied to one or more faces of thenonelastic end portions. However, the pressure-sensitive adhesive coated(or mechanical fastener containing) end portion for releasable attachingto the diaper front portion could be 8 to 15 mm wide while the endportion permanently attached to the diaper side is widenedsubstantially, as disclosed in U.S. Pat. No. 5,399,219.

The present invention may also be used in an extensible elastic tabdesigned to be adhered to the edge of an article, formed using acoextruded elastic film comprising at least one elastic layer and atleast one second layer on at least a first face of the elastic layer,such as described in U.S. Pat. No. 6,159,584, which is hereinincorporated by reference. One face of the coextruded elastic film isattached to at least a partially extensible nonwoven layer: Thepartially expandable, or extensible nonwoven layer has at least onefirst portion with limited extensibility in a first direction and atleast one second inextensible portion in the first direction. Theextensible elastic tab when stretched to the extension limit of thefirst portion or portions in the first direction will elasticallyrecover at least 1.0 cm, preferably at least 2 cm providing an elastictab having a Useful Stretch Ratio (as defined in the Examples of U.S.Pat. No. 6,159,584) of at least 30 percent. The Useful Stretch Ratioincludes the portion of the elastic recovery length having an elasticrecovery force of greater than 20 grams/cm force, but below a givenextension which generally is 90 percent of the extension limit. Further,the elastic tab in the region of the Useful Stretch Ratio preferably hasan incremental extension force of less than about 300 grams/cm. Thecoextruded elastic film second layer is preferably a relativelyinelastic material or blend and provided on both faces of the at leastone elastic layer.

The present invention may also be used in pressure sensitive adhesivebacked tape, such as that described in U.S. Pat. No. 5,800,903, which isherein incorporated by reference in its entirety.

The composition of the present invention may also be used in a thinmulti-layer elastic film that stretches in the transverse direction,such as described in U.S. Pat. No. 6,472,084, which is hereinincorporated by reference. The elastic film has a first layer, a secondlayer and a core layer. The film has activated zones and non-activatedzones. The activated zones have sufficient elasticity to stretch to atleast 200% while maintaining a permanent set percent of no more than 5%.The non-activated zones have sufficient non-elasticity to stretch atleast 200% while maintaining a permanent set percent of up to 5%. Theactivated zones have a tear strength as measured by the Elmendorf TearTest of 30 g while the non-activated zones have a tear strength asmeasured by the Elmendorf Tear Test of at least 50 g. The elastic filmis particularly useful in products such as elastic waistbands , sidepanels and the like for use in products such as absorbent, disposableproducts. The superior tear-strength of the film prevents tearing duringuse of the film and promotes longer-lasting applications of the film. Inaddition, the superior tear-strength of the film prevents existing tearsfrom propagating throughout the film.

The high performance elastic behavior is defined by tensile set lessthan about 50 percent and force relaxation less than about 20 percentafter 300 percent elongation. The procedure to measure hysteresis of asample is as follows:

1. A sample of the film or laminate (6 inches long and 1 inch widestrip) is prepared with the length in the intended direction of use. Thesample is placed lengthwise in the jaws (separated by 4 inches) of atensile testing machine.

2. The sample is pulled a first time (cycle 1 elongation) at the rate of20 inches per minute to the desired elongation (for example, 200percent)

3. The force upon reaching the desired elongation is noted.

4. The sample is held at the desired elongation for 30 seconds afterwhich the force is noted.

5. The instrument is returned to its initial position (zero elongation)

6. The sample is held in a relaxed state for 30 seconds.

7. The sample is pulled a second time (cycle 2 elongation) at the rateof 20 inches per minute to the desired elongation. The amount ofmovement in the tensile testing machine jaw before the film exerts anyforce is noted.

8. The sample is held at the desired elongation for 30 seconds and thenrelaxed.

Tensile set is a measure of the permanent deformation of the sample as aresult of the initial elongation, hold, and relax cycle. Specifically,tensile set is the elongation measured in the second cycle divided bythe initial sample length (2 inches).

When the inventive blend is used in multilayer structures such as thosedescribed within U.S. Pat. No. 6,472,084 B1 the overall structure ismeasured using the Elmendorf Tear Test in accordance with ASTM D 1922,entitled Standard Test Method for Propagation Tear Resistance of PlasticFilm and Thin Sheeting by Pendulum Method.

The following examples are presented to exemplify embodiments of theinvention. All numerical values are approximate. When numerical rangesare given, it should be understood that embodiments outside the statedranges may still fall within the scope of the invention. Specificdetails described in each example should not be construed as necessaryfeatures of the invention.

EXAMPLES

Testing Methods

In the examples that follow, the following analytical techniques areemployed:

GPC Method for Samples 1-4 and A-C

An automated liquid-handling robot equipped with a heated needle set to160° C. is used to add enough 1,2,4-trichlorobenzene stabilized with 300ppm lonol to each dried polymer sample to give a final concentration of30 mg/mL. A small glass stir rod is placed into each tube and thesamples are heated to 160° C. for 2 hours on a heated, orbital-shakerrotating at 250 rpm. The concentrated polymer solution is then dilutedto 1 mg/ml using the automated liquid-handling robot and the heatedneedle set to 160° C.

A Symyx Rapid GPC system is used to determine the molecular weight datafor each sample. A Gilson 350 pump set at 2.0 ml/min flow rate is usedto pump helium-purged 1,2-dichlorobenzene stabilized with 300 ppm lonolas the mobile phase through three Plgel 10 micrometer (μm) Mixed B 300mm×7.5 mm columns placed in series and heated to 160° C. A Polymer LabsELS 1000 Detector is used with the Evaporator set to 250° C., theNebulizer set to 165° C., and the nitrogen flow rate set to 1.8 SLM at apressure of 60-80 psi (400-600 kPa) N₂. The polymer samples are heatedto 160° C. and each sample injected into a 250 μl loop using theliquid-handling robot and a heated needle. Serial analysis of thepolymer samples using two switched loops and overlapping injections areused. The sample data is collected and analyzed using Symyx Epoch™software. Peaks are manually integrated and the molecular weightinformation reported uncorrected against a polystyrene standardcalibration curve.

Standard CRYSTAF Method

Branching distributions are determined by crystallization analysisfractionation (CRYSTAF) using a CRYSTAF 200 unit commercially availablefrom PolymerChar, Valencia, Spain. The samples are dissolved in 1,2,4trichlorobenzene at 160° C. (0.66 mg/mL) for 1 hr and stabilized at 95°C. for 45 minutes. The sampling temperatures range from 95 to 30° C. ata cooling rate of 0.2° C./min. An infrared detector is used to measurethe polymer solution concentrations. The cumulative solubleconcentration is measured as the polymer crystallizes while thetemperature is decreased. The analytical derivative of the cumulativeprofile reflects the short chain branching distribution of the polymer.

The CRYSTAF peak temperature and area are identified by the peakanalysis module included in the CRYSTAF Software (Version 2001.b,PolymerChar, Valencia, Spain). The CRYSTAF peak finding routineidentifies a peak temperature as a maximum in the dW/dT curve and thearea between the largest positive inflections on either side of theidentified peak in the derivative curve. To calculate the CRYSTAF curve,the preferred processing parameters are with a temperature limit of 70°C. and with smoothing parameters above the temperature limit of 0.1, andbelow the temperature limit of 0.3.

DSC Standard Method (Excluding Samples 1-4 and A-C)

Differential Scanning Calorimetry results are determined using a TAImodel Q1000 DSC equipped with an RCS cooling accessory and anautosampler. A nitrogen purge gas flow of 50 ml/min is used. The sampleis pressed into a thin film and melted in the press at about 175° C. andthen air-cooled to room temperature (25° C.). 3-10 mg of material isthen cut into a 6 mm diameter disk, accurately weighed, placed in alight aluminum pan (ca 50 mg), and then crimped shut. The thermalbehavior of the sample is investigated with the following temperatureprofile. The sample is rapidly heated to 1 80° C. and held isothermalfor 3 minutes in order to remove any previous thermal history. Thesample is then cooled to −40° C. at 10° C./min cooling rate and held at−40° C. for 3 minutes. The sample is then heated to 150° C. at 10°C./min. heating rate. The cooling and second heating curves arerecorded.

The DSC melting peak is measured as the maximum in heat flow rate (W/g)with respect to the linear baseline drawn between −30° C. and end ofmelting. The heat of fusion is measured as the area under the meltingcurve between -30° C. and the end of melting using a linear baseline.

GPC Method (Excluding Samples 14 and A-C)

The gel permeation chromatographic system consists of either a PolymerLaboratories Model PL-210 or a Polymer Laboratories Model PL-220instrument. The column and carousel compartments are operated at 140° C.Three Polymer Laboratories 10-micron Mixed-B columns are used. Thesolvent is 1,2,4 trichlorobenzene. The samples are prepared at aconcentration of 0.1 grams of polymer in 50 milliliters of solventcontaining 200 ppm of butylated hydroxytoluene (BHT). Samples areprepared by agitating lightly for 2 hours at 160° C. The injectionvolume used is 100 microliters and the flow rate is 1.0 ml/minute.

Calibration of the GPC column set is performed with 21 narrow molecularweight distribution polystyrene standards with molecular weights rangingfrom 580 to 8,400,000, arranged in 6 “cocktail” mixtures with at least adecade of separation between individual molecular weights. The standardsare purchased from Polymer Laboratories (Shropshire, UK). Thepolystyrene standards are prepared at 0.025 grams in 50 milliliters ofsolvent for molecular weights equal to or greater than 1,000,000, and0.05 grams in 50 milliliters of solvent for molecular weights less than1,000,000. The polystyrene standards are dissolved at 80° C. with gentleagitation for 30 minutes. The narrow standards mixtures are run firstand in order of decreasing highest molecular weight component tominimize degradation. The polystyrene standard peak molecular weightsare converted to polyethylene molecular weights using the followingequation (as described in Williams and Ward, J. Polym. Sci. Polym. Let.,6, 621 (1968)): M_(polyethylene)=0.431 (M_(polystyrene)).

Polyethylene equivalent molecular weight calculations are performedusing Viscotek TriSEC software Version 3.0.

Compression Set

Compression set is measured according to ASTM D 395. The sample isprepared by stacking 25.4 mm diameter round discs of 3.2 mm, 2.0 mm, and0.25 mm thickness until a total thickness of 12.7 mm is reached. Thediscs are cut from 12.7 cm×12.7 cm compression molded plaques moldedwith a hot press under the following conditions: zero pressure for 3 minat 190° C., followed by 86 MPa for 2 min at 190° C., followed by coolinginside the press with cold running water at 86 MPa.

Density

Samples for density measurement are prepared according to ASTM D 1928.Measurements are made within one hour of sample pressing using ASTMD792, Method B.

Flexural/Secant Modulus/ Storage Modulus

Samples are compression molded using ASTM D 1928. Flexural and 2 percentsecant moduli are measured according to ASTM D-790. Storage modulus ismeasured according to ASTM D 5026-01 or equivalent technique.

Optical Properties

Films of 0.4 mm thickness are compression molded using a hot press(Carver Model #4095-4PR1001R). The pellets are placed betweenpolytetrafluoroethylene sheets, heated at 190° C. at 55 psi (380 kPa)for 3 min, followed by 1.3 MPa for 3 min, and then 2.6 MPa for 3 min.The film is then cooled in the press with running cold water at 1.3 MPafor 1 min. The compression molded films are used for opticalmeasurements, tensile behavior, recovery, and stress relaxation.

Clarity is measured using BYK Gardner Haze-gard as specified in ASTM D1746.

45° gloss is measured using BYK Gardner Glossmeter Microgloss 45° asspecified in ASTM D-2457

Internal haze is measured using BYK Gardner Haze-gard based on ASTM D1003 Procedure A. Mineral oil is applied to the film surface to removesurface scratches.

Mechanical Properties—Tensile, Hysteresis, and Tear

Stress-strain behavior in uniaxial tension is measured using ASTM D 1708microtensile specimens. Samples are stretched with an Instron at 500%min⁻¹ at 21° C. Tensile strength and elongation at break are reportedfrom an average of 5 specimens. 300% Hysteresis and Tensile Tests atAmbient Conditions

Inventive and comparative examples (Tables 19, 20, 21, 22) wereformulated by weighing out the components. They were then introduced tothe Haake mixer preheated to 190° C. and set at 40 rpm rotor speed.After torque reached steady state (typically three to five minutes), thesample was then removed and allowed to cool. The blends were then moldedin following method.

Compression molded plaques are prepared by weighing out the necessaryamount of material to fill a 9 inch long by 6 inch wide by 0.5millimeter thick mold. The material and the mold are lined with Mylarfilm and placed between chrome coated metal sheets and then the ensembleis placed into a PHI laminating press model PW-L425 (City of Industry,Calif.) preheated to 190° C. The material is allowed to melt for 5minutes under minimal pressure. Then a force of 10000 pounds is appliedfor 5 minutes. Next, the force is increased to 20000 pounds and 1 minuteis allowed to elapse. Afterwards, the ensemble is placed between 25° C.water-cooled platens and cooled for 5 minutes. The molded plaque is thenremoved from the mold and is aged at ambient conditions (about 20° C.,50% relative humidity) for at least 24 hours before testing.

The 300% hysteresis test at ambient conditions is performed at about 20°C. with 50% relative humidity using an Instron™ 5564 (Canton,Massachusetts) equipped with pneumatic grips and fitted with a 2 kNpound tension load cell. Compression molded plaques are preparedaccording to the compression molding aforementioned procedure.Microtensile specimens (ASTM D1708) are extracted of the compressionmolded plaques using a NAEF (Bolton Landing, New York) B-36 punch. Afterproper calibration of the load cell, the microtensile (ASTM 1708)specimen is oriented parallel to the displacement direction of thecrosshead and then is gripped using a grip separation of 22.25 mm. Thisseparation of 22.25 mm is also taken as the gauge length of the sample.The sample is then stretched to 300% strain at a rate of 500 % min⁻¹(111.25 mm/min). The crosshead direction is then immediately reversed atthen returned to the starting grip separation also at 500 % min⁻¹(111.25 mm/min). The crosshead direction is then again reversed suchthat the sample is then extended at 500 % min⁻¹ (111.25 mm/min). Duringthis loading step, the strain corresponding to a tensile stress of 0.05MPa (megapascals) is taken as the permanent set.

The tensile test at ambient conditions is performed at about 20° C. with50% relative humidity. Specimens are prepared according to thecompression molding procedure described above. An Instron™ 5564 (Canton,Mass.) equipped with pneumatic grips and fitted with a 2 kN poundtension load cell is used. Microtensile specimens (ASTM D1708) areextracted of the compression molded plaques using a NAEF (BoltonLanding, N.Y.) B-36 punch. After proper calibration of the load cell,the microtensile (ASTM 1708) specimen is oriented parallel to thedisplacement direction of the crosshead and then is gripped using a gripseparation of 22.25 mm. This separation of 22.25 mm is also taken as thegauge length of the sample. The sample is then stretched at a rate of500 % min⁻¹ (111.25 mm/min) until the specimen breaks. The peak tensilestress is taken as the tensile strength of the material. Thecorresponding strain is taken as the elongation at break.

Strain is measured as a percentage and is defined as the crossheaddisplacement divided by the original grip separation of 22.25 mm andthen multiplied by 100. Stress is defined as force divided by the crosssectional area of the narrow portion of the gauge portion of the ASTM D1708 microtensile specimen prior to deformation.

Uncertainty for tensile strength measurements is estimated to be aboutless than 20% of the measured values.

Uncertainty for elongation to break measurements is estimated to beabout less than 20% of the measured values.

Uncertainty for 2% secant modulus is estimated to be about less than 30%of the measured values.

Uncertainty for permanent set measurements is estimated to be about +5%strain.

TMA

Thermal Mechanical Analysis (Penetration Temperature) is conducted on30mm diameter x 3.3 mm thick, compression molded discs, formed at 1 80°C. and 10 MPa molding pressure for 5 minutes and then air quenched. Theinstrument used is a Perkin-Elmer TMA 7. In the test, a probe with 1.5mm radius tip (P/N N519-0416) is applied to the surface of the sampledisc with IN force. The temperature is raised at 5° C./min from 25° C.The probe penetration distance is measured as a function of temperature.The experiment ends when the probe has penetrated 1 mm into the sample.

DMA

Dynamic Mechanical Analysis (DMA) is measured on compression moldeddisks formed in a hot press at 1 80° C. at 10 MPa pressure for 5 minutesand then water cooled in the press at 90° C./min. Testing is conductedusing an ARES controlled strain rheometer (TA Instruments) equipped withdual cantilever fixtures for torsion testing.

A 1.5 mm plaque is pressed and cut in a bar of dimensions 32×12 mm. Thesample is clamped at both ends between fixtures separated by 10 mm (gripseparation ΔL) and subjected to successive temperature steps from −100°C. to 200° C. (5° C. per step). At each temperature the torsion modulusG′ is measured at an angular frequency of 10 rad/s, the strain amplitudebeing maintained between 0.1 percent and 4 percent to ensure that thetorque is sufficient and that the measurement remains in the linearregime.

An initial static force of 10 g is maintained (auto-tension mode) toprevent slack in the sample when thermal expansion occurs. As aconsequence, the grip separation ΔL increases with the temperature,particularly above the melting or softening point of the polymer sample.The test stops at the maximum temperature or when the gap between thefixtures reaches 65 mm.

Melt Index

Melt index, or 12, is measured in accordance with ASTM D 1238, Condition190° C./2.16 kg. Melt index, or 110 is also measured in accordance withASTM D 1238, Condition 190° C./10 kg.

Melt Flow Rate

Melt flow rate, or MFR, is measured in accordance with ASTM D 1238,Condition 230° C./2.16 kg.

ATREF

Analytical temperature rising elution fractionation (ATREF) analysis isconducted according to the method described in U.S. Pat. No. 4,798,081and Wilde, L.; Ryle, T. R.;. Knobeloch, D. C.; Peat, I. R.;Determination of Branching Distributions in Polyethylene and EthyleneCopolymers, J. Polym. Sci., 20, 441-455 (1982), which are incorporatedby reference herein in their entirety. The composition to be analyzed isdissolved in trichlorobenzene and allowed to crystallize in a columncontaining an inert support (stainless steel shot) by slowly reducingthe temperature to 20° C. at a cooling rate of 0.1° C./min. The columnis equipped with an infrared detector. An ATREF chromatogram curve isthen generated by eluting the crystallized polymer sample from thecolumn by slowly increasing the temperature of the eluting solvent(trichlorobenzene) from 20 to 120° C. at a rate of 1.5° C./min.

¹³C NMR Analysis

The samples are prepared by adding approximately 3g of a 50/50 mixtureof tetrachloroethane-d²/orthodichlorobenzene to 0.4 g sample in a 10 mmNMR tube. The samples are dissolved and homogenized by heating the tubeand its contents to 150° C. The data are collected using a JEOLEclipseTm 400MHz spectrometer or a Varian Unity PlUSTM 400MHzspectrometer, corresponding to a ¹³C resonance frequency of 100.5 MHz.The data are acquired using 4000 transients per data file with a 6second pulse repetition delay. To achieve minimum signal-to-noise forquantitative analysis, multiple data files are added together. Thespectral width is 25,000 Hz with a minimum file size of 32K data points.The samples are analyzed at 130° C. in a 10 mm broad band probe. Thecomonomer incorporation is determined using Randall's triad method(Randall, J. C.; JMS-Rev. Macromol. Chem. Phys., C29, 201-317 (1989),which is incorporated by reference herein in its entirety.

Polymer Fractionation by TREF

Large-scale TREF fractionation is carried by dissolving 15-20 g ofpolymer in 2 liters of 1,2,4-trichlorobenzene (TCB) by stirring for 4hours at 160° C. The polymer solution is forced by 15 psig (100 kPa)nitrogen onto a 3 inch by 4 foot (7.6 cm×12 cm) steel column packed witha 60:40 (v:v) mix of 30-40 mesh (600-425 μm) spherical, technicalquality glass beads (available from Potters Industries, HC 30 Box 20,Brownwood, Tex., 76801) and stainless steel, 0.028″ (0.7 mm) diametercut wire shot (available from Pellets, Inc. 63 Industrial Drive, NorthTonawanda, N.Y., 14120). The column is immersed in a thermallycontrolled oil jacket, set initially to 160° C. The column is firstcooled ballistically to 125° C., then slow cooled to 20° C. at 0.04° C.per minute and held for one hour. Fresh TCB is introduced at about 65ml/min while the temperature is increased at 0.167° C. per minute.

Approximately 2000 ml portions of eluant from the preparative TREFcolumn are collected in a 16 station, heated fraction collector. Thepolymer is concentrated in each fraction using a rotary evaporator untilabout 50 to 100 ml of the polymer solution remains. The concentratedsolutions are allowed to stand overnight before adding excess methanol,filtering, and rinsing (approx. 300-500 ml of methanol including thefinal rinse). The filtration step is performed on a 3 position vacuumassisted filtering station using 5.0 μm polytetrafluoroethylene coatedfilter paper (available from Osmonics Inc., Cat# Z50WP04750). Thefiltrated fractions are dried overnight in a vacuum oven at 60° C. andweighed on an analytical balance before further testing.

Melt Strength

Melt Strength (MS) is measured by using a capillary rheometer fittedwith a 2.1 mm diameter, 20:1 die with an entrance angle of approximately45 degrees. After equilibrating the samples at 190° C. for 10 minutes,the piston is run at a speed of 1 inch/minute (2.54 cm/minute). Thestandard test temperature is 190° C. The sample is drawn uniaxially to aset of accelerating nips located 100 mm below the die with anacceleration of 2.4 mm/sec . The required tensile force is recorded as afunction of the take-up speed of the nip rolls. The maximum tensileforce attained during the test is defined as the melt strength. The meltstrength is recorded in centiNewtons (“cN”).

Preparation and Properties of Olefin Block Copolymers Catalysts

The term “overnight”, if used, refers to a time of approximately 16-18hours, the term “room temperature”, refers to a temperature of 20-25°C., and the term “mixed alkanes” refers to a commercially obtainedmixture of C₆₋₉ aliphatic hydrocarbons available under the tradedesignation Isopar E®, from ExxonMobil Chemical Company. In the eventthe name of a compound herein does not conform to the structuralrepresentation thereof, the structural representation shall control. Thesynthesis of all metal complexes and the preparation of all screeningexperiments were carried out in a dry nitrogen atmosphere using dry boxtechniques. All solvents used were HPLC grade and were dried beforetheir use.

MMAO refers to modified methylalumoxane, a triisobutylaluminum modifiedmethylalumoxane available commercially from Akzo-Nobel.

The preparation of catalyst (B 1) is conducted as follows. a)Preparation of(1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)methylimine3,5-Di-t-butylsalicylaldehyde (3.00 g) is added to 10 mL ofisopropylamine. The solution rapidly turns bright yellow. After stirringat ambient temperature for 3 hours, volatiles are removed under vacuumto yield a bright yellow, crystalline solid (97 percent yield).

b) Preparation of1,2-bis-(3,5-di-t-butylphenylene)(1-(N-(1-methylethyl)immino)methyl)(2-oxoyl)zirconium dibenzyl

A solution of (1-methylethyl)(2-hydroxy-3,5-di(t-butyl)phenyl)imine (605mg, 2.2 mmol) in 5 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (500 mg, 1.1 mmol) in 50 mL toluene. The resulting darkyellow solution is stirred for 30 min. Solvent is removed under reducedpressure to yield the desired product as a reddish-brown solid.

The preparation of catalyst (B2) is conducted as follows.

a) Preparation of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine

2-Methylcyclohexylamine (8.44 mL, 64.0 mmol) is dissolved in methanol(90 mL), and di-t-butylsalicaldehyde (10.00 g, 42.67 mmol) is added. Thereaction mixture is stirred for three hours and then cooled to −25° C.for 12 hrs. The resulting yellow solid precipitate is collected byfiltration and washed with cold methanol (2×15 mL), and then dried underreduced pressure. The yield is 11.17 g of a yellow solid. 1 H NMR isconsistent with the desired product as a mixture of isomers.

b) Preparation ofbis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconiumdibenzyl

A solution of(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)imine (7.63g, 23.2 mmol) in 200 mL toluene is slowly added to a solution ofZr(CH₂Ph)₄ (5.28 g, 11.6 mmol) in 600 mL toluene. The resulting darkyellow solution is stirred for 1 hour at 25° C. The solution is dilutedfurther with 680 mL toluene to give a solution having a concentration of0.00783 M.

Cocatalyst 1 A mixture of methyldi(C₁₄₋₁₈ alkyl)ammonium salts oftetrakis(pentafluorophenyl)borate (here-in-after armeenium borate),prepared by reaction of a long chain trialkylamine (Armeen™ M2HT,available from Akzo-Nobel), HCl and Li[B(C6F₅)₄], substantially asdisclosed in U.S. Pat. No. 5,919,9883, Ex. 2.

Cocatalyst 2 Mixed C₁₄₋₁₈ alkyldimethylammonium salt ofbis(tris(pentafluorophenyl)-alumane)-2-undecylimidazolide, preparedaccording to U.S. Pat. No. 6,395,671, Ex. 16.

Shuttling Agents The shuttling agents employed include diethylzinc (DEZ,SA1), di(i-butyl)zinc (SA2), di(n-hexyl)zinc (SA3), triethylaluminum(TEA, SA4), trioctylaluminum (SA5), triethylgallium (SA6),i-butylaluminum bis(dimethyl(t-butyl)siloxane) (SA7), i-butylaluminumbis(di(trimethylsilyl)amide) (SA8), n-octylaluminumdi(pyridine-2-methoxide) (SA9), bis(n-octadecyl)i-butylaluminum (SA 10),i-butylaluminum bis(di(n-pentyl)amide) (SA11), n-octylaluminumbis(2,6-di-t-butylphenoxide) (SA 12), n-octylaluminumdi(ethyl(1-naphthyl)amide) (SA 13), ethylaluminumbis(t-butyldimethylsiloxide) (SA14), ethylaluminumdi(bis(trimethylsilyl)amide) (SA 15), ethylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA 16), n-octylaluminumbis(2,3,6,7-dibenzo-1-azacycloheptaneamide) (SA1 7), n-octylaluminumbis(dimethyl(t-butyl)siloxide(SA18), ethylzinc (2,6-diphenylphenoxide)(SA 19), and ethylzinc (t-butoxide) (SA20).

Examples 1-4, Comparative A-C

General High Throughput Parallel Polymerization Conditions

Polymerizations are conducted using a high throughput, parallelpolymerization reactor (PPR) available from Symyx Technologies, Inc. andoperated substantially according to U.S. Pat Nos. 6,248,540, 6,030,917,6,362,309, 6,306,658, and 6,316,663. Ethylene copolymerizations areconducted at 130° C. and 200 psi (1.4 MPa) with ethylene on demand using1.2 equivalents of Cocatalyst 1 based on total catalyst used (1.1equivalents when MMAO is present). A series of polymerizations areconducted in a parallel pressure reactor (PPR) contained of 48individual reactor cells in a 6×8 array that are fitted with apre-weighed glass tube. The working volume in each reactor cell is 6000μL. Each cell is temperature and pressure controlled with stirringprovided by individual stirring paddles. The monomer gas and quench gasare plumbed directly into the PPR unit and controlled by automaticvalves. Liquid reagents are robotically added to each reactor cell bysyringes and the reservoir solvent is mixed alkanes. The order ofaddition is mixed alkanes solvent (4 ml), ethylene, 1-octene comonomer(1 ml), Cocatalyst 1 or Cocatalyst I/MMAO mixture, shuttling agent, andcatalyst or catalyst mixture. When a mixture of Cocatalyst 1 and MMAO ora mixture of two catalysts is used, the reagents are premixed in a smallvial immediately prior to addition to the reactor. When a reagent isomitted in an experiment, the above order of addition is otherwisemaintained. Polymerizations are conducted for approximately 1-2 minutes,until predetermined ethylene consumptions are reached. After quenchingwith CO, the reactors are cooled and the glass tubes are unloaded. Thetubes are transferred to a centrifuge/vacuum drying unit, and dried for12 hours at 60° C. The tubes containing dried polymer are weighed andthe difference between this weight and the tare weight gives the netyield of polymer. Results are contained in Table 1. In Table 1 andelsewhere in the application, comparative compounds are indicated by anasterisk (*).

Examples 1-4 demonstrate the synthesis of linear block copolymers by thepresent invention as evidenced by the formation of a very narrow MWD,essentially monomodal copolymer when DEZ is present and a bimodal, broadmolecular weight distribution product (a mixture of separately producedpolymers) in the absence of DEZ. Due to the fact that Catalyst (A1) isknown to incorporate more octene than Catalyst (B1), the differentblocks or segments of the resulting copolymers of the invention aredistinguishable based on branching or density. TABLE 1 Cat. (A1) Cat(B1) Cocat MMAO shuttling Ex. (μmol) (μmol) (μmol) (μmol) agent (μmol)Yield (g) Mn Mw/Mn hexyls¹ A* 0.06 — 0.066 0.3 — 0.1363 300502 3.32 — B*— 0.1 0.110 0.5 — 0.1581 36957 1.22 2.5 C* 0.06 0.1 0.176 0.8 — 0.203845526 5.30² 5.5 1 0.06 0.1 0.192 — DEZ (8.0) 0.1974 28715 1.19 4.8 20.06 0.1 0.192 — DEZ (80.0) 0.1468 2161 1.12 14.4 3 0.06 0.1 0.192 — TEA(8.0) 0.208 22675 1.71 4.6 4 0.06 0.1 0.192 — TEA (80.0) 0.1879 33381.54 9.4¹C₆ or higher chain content per 1000 carbons²Bimodal molecular weight distribution

It may be seen that the olefin block copolymers produced according tothe invention have a relatively narrow polydispersity (Mw/Mn) and largerblock-copolymer content (trimer, tetramer, or larger) than polymersprepared in the absence of the shuttling agent.

Further characterizing data for the polymers of Table 1 are determinedby reference to the Figures. More specifically DSC and ATREF resultsshow the following:

The DSC curve for the polymer of Example 1 shows a 115.7° C. meltingpoint (Tm) with a heat of fusion of 158.1 J/g. The corresponding CRYSTAFcurve shows the tallest peak at 34.5° C. with a peak area of 52.9percent. The difference between the DSC Tm and the Tcrystaf is 81.2° C.

The DSC curve for the polymer of Example 2 shows a peak with a 109.7° C.melting point (Tm) with a heat of fusion of 214.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 46.2° C. with a peak area of57.0 percent. The difference between the DSC Tm and the Tcrystaf is63.5° C.

The DSC curve for the polymer of Example 3 shows a peak with a 120.7° C.melting point (Tm) with a heat of fusion of 160.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 66.1° C. with a peak area of71.8 percent. The difference between the DSC Tm and the Tcrystaf is54.6° C.

The DSC curve for the polymer of Example 4 shows a peak with a 104.5° C.melting point (Tm) with a heat of fusion of 170.7 J/g. The correspondingCRYSTAF curve shows the tallest peak at 30° C. with a peak area of 18.2percent. The difference between the DSC Tm and the Tcrystaf is 74.5° C.

The DSC curve for Comparative A shows a 90.0° C. melting point (Tm) witha heat of fusion of 86.7 J/g. The corresponding CRYSTAF curve shows thetallest peak at 48.5° C. with a peak area of 29.4 percent. Both of thesevalues are consistent with a resin that is low in density. Thedifference between the DSC Tm and the Tcrystaf is 41.8° C.

The DSC curve for Comparative B shows a 129.8° C. melting point (Tm)with a heat of fusion of 237.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 82.4° C. with a peak area of 83.7 percent.Both of these values are consistent with a resin that is high indensity. The difference between the DSC Tm and the Tcrystaf is 47.4° C.

The DSC curve for Comparative C shows a 125.3° C. melting point (Tm)with a heat of fusion of 143.0 J/g. The corresponding CRYSTAF curveshows the tallest peak at 81.8° C. with a peak area of 34.7 percent aswell as a lower crystalline peak at 52.4° C. The separation between thetwo peaks is consistent with the presence of a high crystalline and alow crystalline polymer. The difference between the DSC Tm and theTcrystaf is 43.5° C.

Examples 5-19 Comparatives D-F Continuous Solution Polymerization,Catalyst A1/B2+DEZ

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil ChemicalCompany), ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, andhydrogen (where used) are supplied to a 3.8 L reactor equipped with ajacket for temperature control and an internal thermocouple. The solventfeed to the reactor is measured by a mass-flow controller. A variablespeed diaphragm pump controls the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst and cocatalyst 1 injection lines and thereactor agitator. These flows are measured by Micro-Motion mass flowmeters and controlled by control valves or by the manual adjustment ofneedle valves. The remaining solvent is combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters and are combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactoris run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer. Process details and results arecontained in Table 2. Selected polymer properties are provided in Table3. TABLE 2 Process Details Cat Cat A1 Cat B2 DEZ Cocat Cocat Poly C₈H₁₆Solv. H₂ T A1² Flow B2³ Flow DEZ Flow Conc. Flow [C₂H₄]/ Rate⁵ Conv Ex.kg/hr kg/hr sccm¹ ° C. ppm kg/hr ppm kg/hr Conc % kg/hr ppm kg/hr [DEZ]⁴kg/hr %⁶ Solids % Eff.⁷ D* 1.63 12.7 29.90 120 142.2  0.14 — — 0.19 0.32 820 0.17 536 1.81 88.8 11.2 95.2 E* ″ 9.5 5.00 ″ — — 109   0.10 0.19 ″1743 0.40 485 1.47 89.9 11.3 126.8 F* ″ 11.3 251.6 ″ 71.7 0.06 30.8 0.06— — ″ 0.11 — 1.55 88.5 10.3 257.7  5 ″ ″ — ″ ″ 0.14 30.8 0.13 0.17 0.43″ 0.26 419 1.64 89.6 11.1 118.3  6 ″ ″ 4.92 ″ ″ 0.10 30.4 0.08 0.17 0.32″ 0.18 570 1.65 89.3 11.1 172.7  7 ″ ″ 21.70 ″ ″ 0.07 30.8 0.06 0.170.25 ″ 0.13 718 1.60 89.2 10.6 244.1  8 ″ ″ 36.90 ″ ″ 0.06 ″ ″ ″ 0.10 ″0.12 1778 1.62 90.0 10.8 261.1  9 ″ ″ 78.43 ″ ″ ″ ″ ″ ″ 0.04 ″ ″ 45961.63 90.2 10.8 267.9 10 ″ ″ 0.00 123 71.1 0.12 30.3 0.14 0.34 0.19 17430.08 415 1.67 90.31 11.1 131.1 11 ″ ″ ″ 120 71.1 0.16 ″ 0.17 0.80 0.151743 0.10 249 1.68 89.56 11.1 100.6 12 ″ ″ ″ 121 71.1 0.15 ″ 0.07 ″ 0.091743 0.07 396 1.70 90.02 11.3 137.0 13 ″ ″ ″ 122 71.1 0.12 ″ 0.06 ″ 0.051743 0.05 653 1.69 89.64 11.2 161.9 14 ″ ″ ″ 120 71.1 0.05 ″ 0.29 ″ 0.101743 0.10 395 1.41 89.42 9.3 114.1 15 2.45 ″ ″ ″ 71.1 0.14 ″ 0.17 ″ 0.141743 0.09 282 1.80 89.33 11.3 121.3 16 ″ ″ ″ 122 71.1 0.10 ″ 0.13 ″ 0.071743 0.07 485 1.78 90.11 11.2 159.7 17 ″ ″ ″ 121 71.1 0.10 ″ 0.14 ″ 0.081743 ″ 506 1.75 89.08 11.0 155.6 18 0.69 ″ ″ 121 71.1 ″ ″ 0.22 ″ 0.111743 0.10 331 1.25 89.93 8.8 90.2 19 0.32 ″ ″ 122 71.1 0.06 ″ ″ ″ 0.091743 0.08 367 1.16 90.74 8.4 106.0*Comparative, not an example of the invention¹ standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dibenzyl⁴molar ratio in reactor⁵polymer production rate⁶percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Zr

TABLE 3 Physical Properties Heat of Tm- CRYSTAF Density Mw Mn FusionT_(m) T_(c) T_(CRYSTAF) T_(CRYSTAF) Peak Area Ex. (g/cm³) I₂ I₁₀ I₁₀/I₂(g/mol) (g/mol) Mw/Mn (J/g) (° C.) (° C.) (° C.) (° C.) (percent) D*0.8627 1.5 10.0 6.5 110,000 55,800 2.0 32 37 45 30 7 99 E* 0.9378 7.039.0 5.6 65,000 33,300 2.0 183 124 113 79 45 95 F* 0.8895 0.9 12.5 13.4137,300 9,980 13.8 90 125 111 78 47 20  5 0.8786 1.5 9.8 6.7 104,60053,200 2.0 55 120 101 48 72 60  6 0.8785 1.1 7.5 6.5 109600 53300 2.1 55115 94 44 71 63  7 0.8825 1.0 7.2 7.1 118,500 53,100 2.2 69 121 103 4972 29  8 0.8828 0.9 6.8 7.7 129,000 40,100 3.2 68 124 106 80 43 13  90.8836 1.1 9.7 9.1 129600 28700 4.5 74 125 109 81 44 16 10 0.8784 1.27.5 6.5 113,100 58,200 1.9 54 116 92 41 75 52 11 0.8818 9.1 59.2 6.566,200 36,500 1.8 63 114 93 40 74 25 12 0.8700 2.1 13.2 6.4 101,50055,100 1.8 40 113 80 30 83 91 13 0.8718 0.7 4.4 6.5 132,100 63,600 2.142 114 80 30 81 8 14 0.9116 2.6 15.6 6.0 81,900 43,600 1.9 123 121 10673 48 92 15 0.8719 6.0 41.6 6.9 79,900 40,100 2.0 33 114 91 32 82 10 160.8758 0.5 3.4 7.1 148,500 74,900 2.0 43 117 96 48 69 65 17 0.8757 1.711.3 6.8 107,500 54,000 2.0 43 116 96 43 73 57 18 0.9192 4.1 24.9 6.172,000 37,900 1.9 136 120 106 70 50 94 19 0.9344 3.4 20.3 6.0 76,80039,400 1.9 169 125 112 80 45 88

The resulting polymers are tested by DSC and ATREF as with previousexamples. Results are as follows:

The DSC curve for the polymer of Example 5 shows a peak with a 119.6° C.melting point (Tm) with a heat of fusion of 60.0 J/g. The correspondingCRYSTAF curve shows the tallest peak at 47.6° C. with a peak area of59.5 percent. The delta between the DSC Tm and the Tcrystaf is 72.0° C.

The DSC curve for the polymer of Example 6 shows a peak with a 115.2° C.melting point (Tm) with a heat of fusion of 60.4 J/g. The correspondingCRYSTAF curve shows the tallest peak at 44.2° C. with a peak area of62.7 percent. The delta between the DSC Tm and the Tcrystaf is 71.0° C.

The DSC curve for the polymer of Example 7 shows a peak with a 121.3° C.melting point with a heat of fusion of 69.1 J/g. The correspondingCRYSTAF curve shows the tallest peak at 49.2° C. with a peak area of29.4 percent. The delta between the DSC Tm and the Tcrystaf is 72.1° C.

The DSC curve for the polymer of Example 8 shows a peak with a 123.5° C.melting point (Tm) with a heat of fusion of 67.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.1° C. with a peak area of12.7 percent. The delta between the DSC Tm and the Tcrystaf is 43.4° C.

The DSC curve for the polymer of Example 9 shows a peak with a 124.6° C.melting point (Tm) with a heat of fusion of 73.5 J/g. The correspondingCRYSTAF curve shows the tallest peak at 80.8° C. with a peak area of16.0 percent. The delta between the DSC Tm and the Tcrystaf is 43.8° C.

The DSC curve for the polymer of Example 10 shows a peak with a 115.6°C. melting point (Tm) with a heat of fusion of 60.7 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 40.9° C. with apeak area of 52.4 percent. The delta between the DSC Tm and the Tcrystafis 74.7° C.

The DSC curve for the polymer of Example 11 shows a peak with a 113.6°C. melting point (Tm) with a heat of fusion of 70.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 39.6° C. with apeak area of 25.2 percent. The delta between the DSC Tm and the Tcrystafis 74.1° C.

The DSC curve for the polymer of Example 12 shows a peak with a 113.2°C. melting point (Tm) with a heat of fusion of 48.9 J/g. Thecorresponding CRYSTAF curve shows no peak equal to or above 30° C.(Tcrystaf for purposes of further calculation is therefore set at 30°C.). The delta between the DSC Tm and the Tcrystaf is 83.2° C.

The DSC curve for the polymer of Example 13 shows a peak with a 114.4°C. melting point (Tm) with a heat of fusion of 49.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 33.8° C. with apeak area of 7.7 percent. The delta between the DSC Tm and the Tcrystafis 84.4° C.

The DSC for the polymer of Example 14 shows a peak with a 120.8° C.melting point (Tm) with a heat of fusion of 127.9 J/g. The correspondingCRYSTAF curve shows the tallest peak at 72.9° C. with a peak area of92.2 percent. The delta between the DSC Tm and the Tcrystaf is 47.9° C.

The DSC curve for the polymer of Example 15 shows a peak with a 114.3°C. melting point (Tm) with a heat of fusion of 36.2 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 32.3° C. with apeak area of 9.8 percent. The delta between the DSC Tm and the Tcrystafis 82.0° C.

The DSC curve for the polymer of Example 16 shows a peak with a 116.6°C. melting point (Tm) with a heat of fusion of 44.9 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 48.0° C. with apeak area of 65.0 percent. The delta between the DSC Tm and the Tcrystafis 68.6° C.

The DSC curve for the polymer of Example 17 shows a peak with a 116.0°C. melting point (Tm) with a heat of fusion of 47.0 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 43.1° C. with apeak area of 56.8 percent. The delta between the DSC Tm and the Tcrystafis 72.9° C.

The DSC curve for the polymer of Example 18 shows a peak with a 120.5°C. melting point (Tm) with a heat of fusion of 141.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 70.0° C. with apeak area of 94.0 percent. The delta between the DSC Tm and the Tcrystafis 50.5° C.

The DSC curve for the polymer of Example 19 shows a peak with a 124.8°C. melting point (Tm) with a heat of fusion of 174.8 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 79.9° C. with apeak area of 87.9 percent. The delta between the DSC Tm and the Tcrystafis 45.0° C.

The DSC curve for the polymer of Comparative D shows a peak with a 37.3°C. melting point (Tm) with a heat of fusion of 31.6 J/g. Thecorresponding CRYSTAF curve shows no peak equal to and above 30° C. Bothof these values are consistent with a resin that is low in density. Thedelta between the DSC Tm and the Tcrystaf is 7.3° C.

The DSC curve for the polymer of Comparative E shows a peak with a 124.0° C. melting point (Tm) with a heat of fusion of 179.3 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 79.3° C. with apeak area of 94.6 percent. Both of these values are consistent with aresin that is high in density. The delta between the DSC Tm and theTcrystaf is 44.6° C.

The DSC curve for the polymer of Comparative F shows a peak with a 124.8° C. melting point (Tm) with a heat of fusion of 90.4 J/g. Thecorresponding CRYSTAF curve shows the tallest peak at 77.6° C. with apeak area of 19.5 percent. The separation between the two peaks isconsistent with the presence of both a high crystalline and a lowcrystalline polymer. The delta between the DSC Tm and the Tcrystaf is47.2° C.

Physical Property Testing

Polymer samples are evaluated for physical properties such as hightemperature resistance properties, as evidenced by TMA temperaturetesting, pellet blocking strength, high temperature recovery, hightemperature compression set and storage modulus ratio, G′(25°C.)/G′(100° C.). Several commercially available polymers are included inthe tests: Comparative G* is a substantially linear ethylene/l-octenecopolymer (AFFINITY®, available from The Dow Chemical Company),Comparative H* is an elastomeric, substantially linear ethylene/1-octenecopolymer (AFFINITY®EG8100, available from The Dow Chemical Company),Comparative I is a substantially linear ethylene/1-octene copolymer(AFFINITY®PL1 840, available from The Dow Chemical Company), ComparativeJ is a hydrogenated styrene/butadiene/styrene triblock copolymer(KRATON™ G1652, available from KRATON Polymers LLC), Comparative K is athermoplastic vulcanizate (TPV, a polyolefin blend containing dispersedtherein a crosslinked elastomer). Results are presented in Table 4.TABLE 4 High Temperature Mechanical Properties 300% Pellet Strain TMA-1mm Blocking Recovery Compression penetration Strength G′(25° C.)/ (80°C.) Set (70° C.) Ex. (° C.) lb/ft² (kPa) G′(100° C.) (percent) (percent)D* 51 — 9 Failed — E* 130 — 18 — — F* 70 141 (6.8)  9 Failed 100   5 1040 (0)  6 81 49  6 110 — 5 — 52  7 113 — 4 84 43  8 111 — 4 Failed 41  997 — 4 — 66 10 108 — 5 81 55 11 100 — 8 — 68 12 88 — 8 — 79 13 95 — 6 8471 14 125 — 7 — — 15 96 — 5 — 58 16 113 — 4 — 42 17 108 0 (0)  4 82 4718 125 — 10 — — 19 133 — 9 — — G* 75 463 (22.2) 89 Failed 100  H* 70 213(10.2) 29 Failed 100  I* 111 — 11 — — J* 107 — 5 Failed 100  K* 152 — 3— 40

In Table 4, Comparative F (which is a physical blend of the two polymersresulting from simultaneous polymerizations using catalyst A1 and B1)has a 1 mm penetration temperature of about 70° C., while Examples 5-9have a 1 mm penetration temperature of 100° C. or greater. Further,examples 10-19 all have a 1 mm penetration temperature of greater than85° C., with most having 1 mm TMA temperature of greater than 90° C. oreven greater than 100° C. This shows that the novel olefin blockcopolymers have better dimensional stability at higher temperaturescompared to a physical blend of homopolymers of the comonomers.Comparative J (a commercial SEBS) has a good 1 mm TMA temperature ofabout 107° C., but it has very poor (high temperature 70° C.)compression set of about 100 percent and it also failed to recover(sample broke) during a high temperature (80° C.) 300 percent strainrecovery. Thus, the exemplified olefin block copolymers have a uniquecombination of properties unavailable even in some commerciallyavailable, high performance thermoplastic elastomers.

Similarly, Table 4 shows a low (good) storage modulus ratio, G′(25°C.)/G′(100° C.), for the inventive olefin block copolymers of 6 or less,whereas a physical blend (Comparative F) has a storage modulus ratio of9 and a random ethylene/octene copolymer (Comparative G) of similardensity has a storage modulus ratio an order of magnitude greater (89).It is desirable that the storage modulus ratio of a polymer be as closeto 1 as possible. Such polymers will be relatively unaffected bytemperature, and fabricated articles made from such polymers can beusefully employed over a broad temperature range. This feature of lowstorage modulus ratio and temperature independence is particularlyuseful in elastomer applications such as in pressure sensitive adhesiveformulations.

The data in Table 4 also demonstrate that the olefin block copolymers ofthe invention possess improved pellet blocking strength. In particular,Example 5 has a pellet blocking strength of 0 MPa, meaning it is freeflowing under the conditions tested, compared to Comparatives F and Gwhich show considerable blocking. Blocking strength is important sincebulk shipment of polymers having large blocking strengths can result inproduct clumping or sticking together upon storage or shipping,resulting in poor handling properties.

High temperature (70° C.) compression set for the inventive olefin blockcopolymers is generally good, meaning generally less than about 80percent, preferably less than about 70 percent and especially less thanabout 60 percent. In contrast, Comparatives F, G, H and J all have a 70°C. compression set of 100 percent (the maximum possible value,indicating no recovery). Good high temperature compression set (lownumerical values) is especially needed for applications such as gaskets,window profiles, o-rings, and the like. TABLE 5 Ambient TemperatureMechanical Properties Tensile 100% 300% Retractive Flex Abrasion:Notched Strain Strain Stress at Com- Stress Mod- Tensile TensileElongation Tensile Elongation Volume Tear Recovery Recovery 150%pression Relaxation ulus Modulus Strength at Break¹ Strength at BreakLoss Strength 21° C. 21° C. Strain Set 21° C. at 50% Ex. (MPa) (MPa)(MPa)¹ (%) (MPa) (%) (mm³) (mJ) (percent) (percent) (kPa) (Percent)Strain² D* 12 5 — — 10 1074 — — 91 83 760 — — E* 895 589 — 31 1029 — — —— — — — F* 57 46 — — 12 824 93 339 78 65 400 42 —  5 30 24 14 951 161116 48 — 87 74 790 14 33  6 33 29 — — 14 938 — — — 75 861 13 —  7 44 3715 846 14 854 39 — 82 73 810 20 —  8 41 35 13 785 14 810 45 461 82 74760 22 —  9 43 38 — — 12 823 — — — — — 25 — 10 23 23 — — 14 902 — — 8675 860 12 — 11 30 26 — — 16 1090 — 976 89 66 510 14 30 12 20 17 12 96113 931 — 1247  91 75 700 17 — 13 16 14 — — 13 814 — 691 91 — — 21 — 14212 160 — — 29 857 — — — — — — — 15 18 14 12 1127  10 1573 — 2074  89 83770 14 — 16 23 20 — — 12 968 — — 88 83 1040  13 — 17 20 18 — — 13 1252 —1274  13 83 920  4 — 18 323 239 — — 30 808 — — — — — — — 19 706 483 — —36 871 — — — — — — — G* 15 15 — — 17 1000 — 746 86 53 110 27 50 H* 16 15— — 15 829 — 569 87 60 380 23 — I* 210 147 — — 29 697 — — — — — — — J* —— — — 32 609 — — 93 96 1900  25 — K* — — — — — — — — — — — 30 —¹Tested at 51 cm/minute²measured at 38° C. for 12 hours

Table 5 shows results for mechanical properties for the new olefin blockcopolymers as well as for various comparison polymers at ambienttemperatures. It may be seen that the inventive polymers have very goodabrasion resistance when tested according to ISO 4649, generally showinga volume loss of less than about 90 mm , preferably less than about 80mm , and especially less than about 50 mm . In this test, higher numbersindicate higher volume loss and consequently lower abrasion resistance.

Tear strength as measured by tensile notched tear strength of theinventive polymers is generally 1000 mJ or higher, as shown in Table 5.Tear strength for the inventive polymers can be as high as 3000 mJ, oreven as high as 5000 mJ. Comparative polymers generally have tearstrengths no higher than 750 mJ.

Table 5 also shows that the polymers of the invention have betterretractive stress at 150 percent strain (demonstrated by higherretractive stress values) than some of the comparative samples.Comparative Examples F, G and H have retractive stress value at 150percent strain of 400 kPa or less, while the inventive polymers haveretractive stress values at 150 percent strain of 500 kPa (Ex. 11) to ashigh as about 1100 kPa (Ex. 17). Polymers having higher than 150 percentretractive stress values would be quite useful for elastic applications,such as elastic fibers and fabrics, especially nonwoven fabrics. Otherapplications include diaper, hygiene, and medical garment waistbandapplications, such as tabs and elastic bands.

Table 5 also shows that stress relaxation (at 50 percent strain) is alsoimproved (less) for the inventive polymers as compared to, for example,Comparative G. Lower stress relaxation means that the polymer retainsits force better in applications such as diapers and other garmentswhere retention of elastic properties over long time periods at bodytemperatures is desired.

Optical Testing TABLE 6 Polymer Optical Properties Ex. Internal Haze(percent) Clarity (percent) 45° Gloss (percent) F* 84 22 49 G* 5 73 56 5 13 72 60  6 33 69 53  7 28 57 59  8 20 65 62  9 61 38 49 10 15 73 6711 13 69 67 12 8 75 72 13 7 74 69 14 59 15 62 15 11 74 66 16 39 70 65 1729 73 66 18 61 22 60 19 74 11 52 G* 5 73 56 H* 12 76 59 I* 20 75 59

The optical properties reported in Table 6 are based on compressionmolded films stantially lacking in orientation. Optical properties ofthe polymers may be varied over wide ranges, due to variation incrystallite size, resulting from variation in the quantity of chainshuttling agent employed in the polymerization.

Extractions of Multi-Block Copolymers

Extraction studies of the polymers of Examples 5, 7 and Comparative Eare conducted. In the experiments, the polymer sample is weighed into aglass fritted extraction thimble and fitted into a Kumagawa typeextractor. The extractor with sample is purged with nitrogen, and a 500mL round bottom flask is charged with 350 mL of diethyl ether. The flaskis then fitted to the extractor. The ether is heated while beingstirred. Time is noted when the ether begins to condense into thethimble, and the extraction is allowed to proceed under nitrogen for 24hours. At this time, heating is stopped and the solution is allowed tocool. Any ether remaining in the extractor is returned to the flask. Theether in the flask is evaporated under vacuum at ambient temperature,and the resulting solids are purged dry with nitrogen. Any residue istransferred to a weighed bottle using successive washes of hexane. Thecombined hexane washes are then evaporated with another nitrogen purge,and the residue dried under vacuum overnight at 40° C.. Any remainingether in the extractor is purged dry with nitrogen.

A second clean round bottom flask charged with 350 mL of hexane is thenconnected to the extractor. The hexane is heated to reflux with stirringand maintained at reflux for 24 hours after hexane is first noticedcondensing into the thimble. Heating is then stopped and the flask isallowed to cool. Any hexane remaining in the extractor is transferredback to the flask. The hexane is removed by evaporation under vacuum atambient temperature, and any residue remaining in the flask istransferred to a weighed bottle using successive hexane washes. Thehexane in the flask is evaporated by a nitrogen purge, and the residueis vacuum dried overnight at 40° C.

The polymer sample remaining in the thimble after the extractions istransferred from the thimble to a weighed bottle and vacuum driedovernight at 40° C. Results are contained in Table 7. TABLE 7 etherether C₈ hexane hexane C₈ residue wt. soluble soluble mole solublesoluble mole C₈ mole Sample (g) (g) (percent) percent¹ (g) (percent)percent¹ percent¹ Comp. 1.097 0.063 5.69 12.2 0.245 22.35 13.6 6.5 F*Ex. 5 1.006 0.041 4.08 — 0.040 3.98 14.2 11.6 Ex. 7 1.092 0.017 1.5913.3 0.012 1.10 11.7 9.9¹Determined by ¹³C NMRAdditional Polymer Examples 19 A-J, Continuous Solution Polymerization,Catalyst A1/B2+DEZ

FOR EXAMPLES 19A-I

Continuous solution polymerizations are carried out in a computercontrolled well-mixed reactor. Purified mixed alkanes solvent (Isopar™ Eavailable from Exxon Mobil Chemical Company) ethylene, 1-octene, andhydrogen (where used) are combined and fed to a 27 gallon reactor. Thefeeds to the reactor are measured by mass-flow controllers. Thetemperature of the feed stream is controlled by use of a glycol cooledheat exchanger before entering the reactor. The catalyst componentsolutions are metered using pumps and mass flow meters. The reactor isrun liquid-full at approximately 550 psig pressure. Upon exiting thereactor, water and additive are injected in the polymer solution. Thewater hydrolyzes the catalysts, and terminates the polymerizationreactions. The post reactor solution is then heated in preparation for atwo-stage devolatization. The solvent and unreacted monomers are removedduring the devolatization process. The polymer melt is pumped to a diefor underwater pellet cutting.

For Example 19J

Continuous solution polymerizations are carried out in a computercontrolled autoclave reactor equipped with an internal stirrer. Purifiedmixed alkanes solvent (Isopar™ E available from ExxonMobil ChemicalCompany), ethylene at 2.70 lbs/hour (1.22 kg/hour), 1-octene, andhydrogen (where used) are supplied to a 3.8 L reactor equipped with ajacket for temperature control and an internal thermocouple. The solventfeed to the reactor is measured by a mass-flow controller. A variablespeed diaphragm pump controls the solvent flow rate and pressure to thereactor. At the discharge of the pump, a side stream is taken to provideflush flows for the catalyst and cocatalyst injection lines and thereactor agitator. These flows are measured by Micro-Motion mass flowmeters and controlled by control valves or by the manual adjustment ofneedle valves. The remaining solvent is combined with 1-octene,ethylene, and hydrogen (where used) and fed to the reactor. A mass flowcontroller is used to deliver hydrogen to the reactor as needed. Thetemperature of the solvent/monomer solution is controlled by use of aheat exchanger before entering the reactor. This stream enters thebottom of the reactor. The catalyst component solutions are meteredusing pumps and mass flow meters and are combined with the catalystflush solvent and introduced into the bottom of the reactor. The reactoris run liquid-full at 500 psig (3.45 MPa) with vigorous stirring.Product is removed through exit lines at the top of the reactor. Allexit lines from the reactor are steam traced and insulated.Polymerization is stopped by the addition of a small amount of waterinto the exit line along with any stabilizers or other additives andpassing the mixture through a static mixer. The product stream is thenheated by passing through a heat exchanger before devolatilization. Thepolymer product is recovered by extrusion using a devolatilizingextruder and water cooled pelletizer.

Process details and results are contained in Table 8. Selected polymerproperties are provided in Tables 9A-C.

In Table 9B, inventive examples 19F and 19G show low immediate set ofaround 65-70 % strain after 500% elongation. TABLE 8 PolymerizationConditions Cat Cat Cat A1² Cat A1 B2³ B2 DEZ DEZ C₂H₄ C₈H₁₆ Solv. H₂ TConc. Flow Conc. Flow Conc Flow Ex. lb/hr lb/hr lb/hr sccm¹ ° C. ppmlb/hr ppm lb/hr wt % lb/hr 19A 55.29 32.03 323.03 101 120 600 0.25 2000.42 3.0 0.70 19B 53.95 28.96 325.3 577 120 600 0.25 200 0.55 3.0 0.2419C 55.53 30.97 324.37 550 120 600 0.216 200 0.609 3.0 0.69 19D 54.8330.58 326.33 60 120 600 0.22 200 0.63 3.0 1.39 19E 54.95 31.73 326.75251 120 600 0.21 200 0.61 3.0 1.04 19F 50.43 34.80 330.33 124 120 6000.20 200 0.60 3.0 0.74 19G 50.25 33.08 325.61 188 120 600 0.19 200 0.593.0 0.54 19H 50.15 34.87 318.17 58 120 600 0.21 200 0.66 3.0 0.70 19I55.02 34.02 323.59 53 120 600 0.44 200 0.74 3.0 1.72 19J 7.46 9.04 50.647 120 150 0.22 76.7 0.36 0.5 0.19 Zn⁴ Cocat 1 Cocat 1 Cocat 2 Cocat 2in Poly Conc. Flow Conc. Flow polymer Rate⁵ Conv⁶ Polymer Ex. ppm lb/hrppm lb/hr ppm lb/hr wt % wt % Eff.⁷ 19A 4500 0.65 525 0.33 248 83.9488.0 17.28 297 19B 4500 0.63 525 0.11 90 80.72 88.1 17.2 295 19C 45000.61 525 0.33 246 84.13 88.9 17.16 293 19D 4500 0.66 525 0.66 491 82.5688.1 17.07 280 19E 4500 0.64 525 0.49 368 84.11 88.4 17.43 288 19F 45000.52 525 0.35 257 85.31 87.5 17.09 319 19G 4500 0.51 525 0.16 194 83.7287.5 17.34 333 19H 4500 0.52 525 0.70 259 83.21 88.0 17.46 312 19I 45000.70 525 1.65 600 86.63 88.0 17.6 275 19J — — — — — — — — —¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dimethyl⁴ppm in final product calculated by mass balance⁵polymer production rate⁶weight percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Z

TABLE 9A Polymer Physical Properties Heat of CRYSTAF Density M_(w) M_(n)Fusion T_(m) T_(c) T_(CRYSTAF) T_(m) − T_(CRYSTAF) Peak Area Ex. (g/cc)I₂ I₁₀ I₁₀/I₂ (g/mol) (g/mol) M_(w)/M_(n) (J/g) (° C.) (° C.) (° C.) (°C.) (wt %) 19A 0.8781 0.9 6.4 6.9 123700 61000 2.0 56 119 97 46 73 4019B 0.8749 0.9 7.3 7.8 133000 44300 3.0 52 122 100 30 92 76 19C 0.87535.6 38.5 6.9 81700 37300 2.2 46 122 100 30 92  8 19D 0.8770 4.7 31.5 6.780700 39700 2.0 52 119 97 48 72  5 19E 0.8750 4.9 33.5 6.8 81800 417002.0 49 121 97 36 84 12 19F 0.8652 1.1 7.5 6.8 124900 60700 2.1 27 119 8830 89 89 19G 0.8649 0.9 6.4 7.1 135000 64800 2.1 26 120 92 30 90 90 19H0.8654 1.0 7.0 7.1 131600 66900 2.0 26 118 88 — — — 19I 0.8774 11.2 75.26.7 66400 33700 2.0 49 119 99 40 79 13 19J 0.8995 5.6 39.4 7.0 7550029900 2.5 101 122 106 — — —

TABLE 9B Polymer Physical Properties of Compression Molded FilmImmediate Immediate Immediate Set after Set after Set after RecoveryRecovery Recovery Density Melt Index 100% Strain 300% Strain 500% Strainafter 100% after 300% after 500% Example (g/cm³) (g/10 min) (%) (%) (%)(%) (%) (%) 19A 0.878 0.9 15 63 131 85 79 74 19B 0.877 0.88 14 49 97 8684 81 19F 0.865 1 — — 70 — 87 86 19G 0.865 0.9 — — 66 — — 87 19H 0.8650.92 — 39 — — 87 —

TABLE 9C Average Block Index for Exemplary Polymers¹ Example Zn/C₂ ²Average BI Polymer F 0 0 Polymer 8 0.56 0.59 Polymer 19a 1.3 0.62Polymer 5 2.4 0.52 Polymer 19b 0.56 0.54 Polymer 19h 3.15 0.59¹Additional information regarding the calculation of the block indicesfor various polymers is disclosed in U.S. patent application Ser. No.11/376,835, entitled “Ethylene/α-Olefin Block Interpolymers”, filed onMar. 15, 2006, in the name of Colin L. P. Shan, Lonnie Hazlitt, et. al.and assigned to Dow Global Technologies Inc., the disclosure of which isincorporated by reference herein in its entirety.²Zn/C₂ * 1000 = (Zn feed flow * Zn concentration/1000000/Mw ofZn)/(Total Ethylene feed flow * (1 − fractional ethylene conversionrate)/Mw of Ethylene) * 1000. Please note that “Zn” in “Zn/C₂ * 1000”refers to the amount of zinc in diethyl zinc (“DEZ”) used in thepolymerization process, and “C2” refers to the amount of ethylene usedin the polymerization process.

Measurement of Weight Percent of Hard and Soft Segments

As discussed above, the block interpolymers comprise hard segments andsoft segments. The soft segments can be present in a block interpolyrnerfrom about 1 weight percent to about 99 weight percent of the totalweight of the block interpolymer, preferably from about 5 weight percentto about 95 weight percent, from about 10 weight percent to about 90weight percent, from about 15 weight percent to about 85 weight percent,from about 20 weight percent to about 80 weight percent, from about 25weight percent to about 75 weight percent, from about 30 weight percentto about 70 weight percent, from about 35 weight percent to about 65weight percent, from about 40 weight percent to about 60 weight percent,or from about 45 weight percent to about 55 weight percent. Conversely,the hard segments can be present in a similar range as above. The softsegment weight percentage (and thus the hard segment weight percentage)can be measured by DSC or NMR.

Hard Segment Weight fraction Measured by DSC

For a block polymer having hard segments and soft segments, the densityof the overall block polymer, Poverall, satisfies the followingrelationship:$\frac{1}{\rho_{overall}} = {\frac{x_{hard}}{\rho_{hard}} + \frac{x_{soft}}{\rho_{soft}}}$

where ρ_(hard), and ρ_(soft), are the theoretical density of the hardsegments and soft segments, respectively. χ_(hard), and χ_(soft), arethe weight fraction of the hard segments and soft segments, respectivelyand they add up to one. Assuming ρ_(hard) is equal to the density ofethylene homopolymer, i.e., 0.96 g/cc, and transposing the aboveequation, one obtains the following equation for the weight fraction ofhard segments:$x_{hard} = \frac{\frac{1}{\rho_{Overall}} - \frac{1}{\rho_{soft}}}{{- \frac{1}{\rho_{Overall}}} + \frac{1}{0.96\quad g\text{/}{cc}}}$

In the above equation, ρ_(overall) can be measured from the blockpolymer. Therefore, ifρ_(soft) is known, the hard segment weightfraction can be calculated accordingly. Generally, the soft segmentdensity has a linear relationship with the soft segment meltingtemperature, which can be measured by DSC over a certain range:ρ_(soft) =A*T _(m) +B

where A and B are constants, and T_(m) is the soft segment meltingtemperature in degrees Celsius. A and B can be determined by running DSCon various copolymers with a known density to obtain a calibrationcurve. It is preferable to create a soft segment calibration curve thatspan the range of composition (both comonomer type and content) presentin the block copolymer. In some embodiments, the calibration curvesatisfies the following relationship:ρ_(soft)=0.00049*T _(m)+0.84990

Therefore, the above equation can be used to calculate the soft segmentdensity if T_(m) in degrees Celsius is known.

For some block copolymers, there is an identifiable peak in DSC that isassociated with the melting of the soft segments. In this case, it isrelatively straightforward to determine Tm for the soft segments. OnceT_(m) in degrees Celsius is determined from DSC, the soft segmentdensity can be calculated and thus the hard segment weight fraction.

For other block copolymers, the peak associated with the melting of thesoft segments is either a small hump (or bump) over the baseline orsometimes not visible as illustrated in FIG. 10. This difficulty can beovercome by converting a normal DSC profile into a weighted DSC profileas shown in FIG. 11. The following method is used to convert a normalDSC profile to a weighted DSC profile.

In DSC, the heat flow depends on the amount of the material melting at acertain temperature as well as on the temperature-dependent specificheat capacity. The temperature-dependence of the specific heat capacityin the melting regime of linear low density polyethylene leads to anincrease in the heat of fusion with decreasing comonomer content. Thatis, the heat of fusion values get progressively lower as thecrystallinity is reduced with increasing comonomer content. See Wild, L.Chang, S.; Shankemarayanan, M J. “Improved method for compositionalanalysis of polyolefins by DSC.” Polym. Prep 1990; 31: 270-1, which isincorporated by reference herein in its entirety.

For a given point in the DSC curve (defined by its heat flow in wattsper gram and temperature in degrees Celsius), by taking the ratio of theheat of fusion expected for a linear copolymer to thetemperature-dependent heat of fusion (ΔH(T)), the DSC curve can beconverted into a weight-dependent distribution curve.

The temperature-dependent heat of fusion curve can be calculated fromthe summation of the integrated heat flow between two consecutive datapoints and then represented overall by the cumulative enthalpy curve.

The expected relationship between the heat of fusion for linearethylene/octene copolymers at a given temperature is shown by the heatof fusion versus melting temperature curve. Using random ethylene/octenecopolymers, one can obtain the following relationship:Melt Enthalpy (J/g) =0.0072*T _(m) ² (° C.)+0.3138*T _(m) (° C.)+8.9767

For each integrated data point, at a given temperature, by taking aratio of the enthalpy from the cumulative enthalpy curve to the expectedheat of fusion for linear copolymers at that temperature, fractionalweights can be assigned to each point of the DSC curve.

It should be noted that, in the above method, the weighted DSC iscalculated in the range from 0° C. until the end of melting. The methodis applicable to ethylene/octene copolymers but can be adapted to otherpolymers.

Applying the above methodology to various polymers, the weightpercentage of the hard segments and soft segments were calculated, whichare listed in Table 10. It should be noted that sometimes it isdesirable to assign 0.94 g/cc to the theoretical hard segment density,instead of using the density for homopolyethylene, due to the fact thatthe hard segments may include a small amount of comonomers. TABLE 10Calculated Weight Percentage of Hard and Soft Segments for VariousPolymers Soft Segment Calculated T_(m) (° C.) from Soft CalculatedCalculated Polymer weighted Segment wt % Hard wt % Example No. OverallDensity DSC Density Segment Soft Segment F* 0.8895 20.3 0.860 32% 68%  50.8786 13.8 0.857 23% 77%  6 0.8785 13.5 0.857 23% 77%  7 0.8825 16.50.858 26% 74%  8 0.8828 17.3 0.858 26% 74%  9 0.8836 17.0 0.858 27% 73%10 0.878 15.0 0.857 22% 78% 11 0.882 16.5 0.858 25% 75% 12 0.870 19.50.859 12% 88% 13 0.872 23.0 0.861 12% 88% 14 0.912 21.8 0.861 54% 46% 150.8719 0.5 0.850 22% 78% 16 0.8758 0.3 0.850 26% 74% 18 0.9192 — — — —19 0.9344 38.0 0.869 74% 26% 17 0.8757 2.8 0.851 25% 75% 19A 0.8777 11.50.856 23% 77% 19B 0.8772 14.3 0.857 22% 78% 19J 0.8995 4.8 0.852 47% 53%

Hard Segment Weight Percentage Measured by NMR

¹³C NMR spectroscopy is one of a number of techniques known in the artfor measuring comonomer incorporation into a polymer. An example of thistechnique is described for the determination of comonomer content forethylene/α-olefin copolymers in Randall (Journal of MacromolecularScience, Reviews in Macromolecular Chemistry and Physics , C29 (2 & 3),201-317 (1989)), which is incorporated by reference herein in itsentirety. The basic procedure for determining the comonomer content ofan ethylene/olefin interpolymer involves obtaining a ¹³C NMR spectrumunder conditions where the intensity of the peaks corresponding to thedifferent carbons in a sample is directly proportional to the totalnumber of contributing nuclei in the sample. Methods for ensuring thisproportionality are known in the art and involve allowance forsufficient time for relaxation after a pulse the use of gated-decouplingtechniques, relaxation agents, and the like. The relative intensity of apeak or group of peaks is obtained in practice from itscomputer-generated integral. After obtaining the spectrum andintegrating the peaks, those peaks associated with the comonomer areassigned. This assignment can be made by reference to known spectra orliterature, or by synthesis and analysis of model compounds, or by theuse of isotopically labeled comonomers. The mole % comonomer can bedetermined by the ratio of the integrals corresponding to the number ofmoles of comonomer to the integrals corresponding to the number of molesof all of the monomers in the interpolymer, as described in theaforementioned Randall reference.

Since the hard segment generally has less than about 2.0 wt % comonomer,its major contribution to the spectrum is only for the integral at about30 ppm. The hard segment contribution to the peaks not at 30 ppm isassumed negligible at the start of the analysis. So for the startingpoint, the integrals of the peaks not at 30 ppm are assumed to come fromthe soft segment only. These integrals are fit to a first orderMarkovian statistical model for copolymers using a linear least squaresminimization, thus generating fitting parameters (i.e., probability ofoctene insertion after octene, P_(oo), and probability of octeneinsertion after ethylene, Peo) that are used to compute the soft segmentcontribution to the 30 ppm peak. The difference between the totalmeasured 30 ppm peak integral and the computed soft segment integralcontribution to the 30 ppm peak is the contribution from the hardsegment. Therefore, the experimental spectrum has now been deconvolutedinto two integral lists describing the soft segment and hard segment,respectively. The calculation of weight percentage of the hard segmentis straight forward and calculated by the ratio of the sum of integralsfor the hard segment spectrum to the sum of integrals for the overallspectrum.

From the deconvoluted soft segment integral list, the comonomercomposition can be calculated according to the method of Randall, forexample. From the comonomer composition of the overall spectrum and thecomonomer composition of the soft segment, one can use mass balance tocompute the comonomer composition of the hard segment. From thecomonomer composition of the hard segment, Bernoullian statistics isused to calculate the contribution of the hard segment to the integralsof non 30 ppm peaks. There is usually so little octene, typically fromabout 0 to about 1 mol %, in the hard segment that Bemoullian statisticsis a valid and robust approximation. These contributions are thensubtracted out from the experimental integrals of the non 30 ppm peaks.The resulting non 30 ppm peak integrals are then fitted to a first orderMarkovian statistics model for copolymers as described in the aboveparagraph. The iterative process is performed in the following manner:fit total non 30 ppm peaks then compute soft segment contribution to 30ppm peak; then compute soft/hard segment split and then compute hardsegment contribution to non 30 ppm peaks; then correct for hard segmentcontribution to non 30 ppm peaks and fit resulting non 30 ppm peaks.This is repeated until the values for soft/hard segment split convergeto a minimum error function. The final comonomer compositions for eachsegment are reported.

Validation of the measurement is accomplished through the analysis ofseveral in situ polymer blends. By design of the polymerization andcatalyst concentrations the expected split is compared to the measuredNMR split values. The soft/hard catalyst concentration is prescribed tobe 74% /26%. The measured value of the soft/hard segment split is 78%/22%. Table 11 shows the chemical shift assignments for ethylene octenepolymers. TABLE 11 Chemical Shift Assignments for Ethylene/OcteneCopolymers.   41-40.6 ppm OOOE/EOOO αα CH2 40.5-40.0 ppm EOOE αα CH238.9-37.9 ppm EOE CH 36.2-35.7 ppm OOE center CH 35.6-34.7 ppm OEO αγ,OOO center 6B, OOEE αδ+, OOE center 6B CH2 34.7-34.1 ppm EOE αδ+, EOE 6BCH2 33.9-33.5 ppm OOO center CH 32.5-32.1 ppm 3B CH2 31.5-30.8 ppm OEEOγγ CH2 30.8-30.3 ppm OE γδ+ CH2 30.3-29.0 ppm 4B, EEE δ+δ+ CH2 28.0-26.5ppm OE βδ+ 5B 25.1-23.9 ppm OEO ββ 23.0-22.6 ppm 2B 14.5-14.0 ppm 1B

The following experimental procedures are used. A sample is prepared byadding 0.25 g in a 10 mm NMR tube with 2.5 mL of stock solvent. Thestock solvent is made by dissolving 1 g perdeuterated1,4-dichlorobenzene in 30 mL ortho-dichlorobenzene with 0.025 M chromiumacetylacetonate (relaxation agent). The headspace of the tube is purgedof oxygen by displacement with pure nitrogen. The sample tube is thenheated in a heating block set at 150° C. The sample tube is repeatedlyvortexed and heated until the solution flows consistently from top ofthe solution column to the bottom. The sample tube is then left in theheat block for at least 24 hours to achieve optimum sample homogeneity.

The ¹³C NMR data is collected using a Varian Inova Unity 400 MHz systemwith probe temperature set at 125° C. The center of the excitationbandwidth is set at 32.5 ppm with spectrum width set at 250 ppm.Acquisition parameters are optimized for quantitation including 90°pulse, inverse gated H decoupling, 1.3 second acquisition time, 6seconds delay time, and 8192 scans for data averaging. The magneticfield is carefully shimmed to generate a line shape of less than 1 Hz atfull width half maximum for the solvent peaks prior to data acquisition.The raw data file is processed using NUTS processing software (availablefrom Acorn NMR, Inc. in Livermore, CA) and a list of integrals isgenerated.

Inventive Polymer 19A is analyzed for the soft/hard segment split andsoft/hard comonomer composition. The following is the list of integralsfor this polymer. The NMR spectrum for Polymer 19A is shown in FIG. 12.Integral limit Integral value 41.0-40.6 ppm 1.067 40.5-40.0 ppm 6.24738.9-37.9 ppm 82.343 36.2-35.7 ppm 14.775 35.6-34.7 ppm 65.563 34.7-34.1ppm 215.518 33.9-33.5 ppm 0.807 32.5-32.1 ppm 99.612 31.5-30.8 ppm14.691 30.8-30.3 ppm 115.246 30.3-29.0 ppm 1177.893 28.0-26.5 ppm258.294 25.1-23.9 ppm 19.707 23.0-22.6 ppm 100 14.5-14.0 ppm 99.895

Using Randall's triad method, the total octene weight percentage in thissample is determined to be 34.6%. Using all the above integralsexcluding the 30.3-29.0 ppm integral to fit a first order Markovianstatistical model, the values for Poo and Peo are determined to be0.08389 and 0.2051, respectively. Using these two parameters, thecalculated integral contribution from the soft segment to the 30 ppmpeak is 602.586. Subtraction of 602.586 from the observed total integralfor the 30 ppm peak, 1177.893, yields the contribution of the hardsegment to the 30 ppm peak of 576.307. Using 576.307 as the integral forthe hard segment, the weight percentage of hard segment is determined tobe 26%. Therefore the soft segment weight percentage is 100-26=74%.Using the above values for P_(oo) and P_(eo), the octene weightpercentage of the soft segment is determined to be 47%. Using theoverall octene weight percentage and the octene weight percentage of thesoft segment as well as the soft segment weight percentage, the octeneweight percentage in the hard segment is calculated to be negative 2 wt%. This value is within the error of the measurement. Thus there is noneed to iterate back to account for hard segment contribution to non 30ppm peaks. Table 12 summarizes the calculation results for Polymers 19A,B, F and G. TABLE 12 Hard and Soft Segments Data for Polymers 19A, B, Fand G wt % wt % octene in wt % Soft Hard Soft Example Segment SegmentSegment 19A 74 26 47 19B 74 26 48 19F 86 14 49 19G 84 16 49

Comparative Examples L-P

Comparative Example L was a f-PVC, i.e., flexible poly(vinyl chloride),(obtained from Wofoo Plastics, Hong Kong, China). Comparative Example Mwas a SBS copolymer, VECTOR™ 7400 (obtained from Dexco Polymers,Houston, Tex.). Comparative Example N was a partially crosslinked TPV,VYRAM™ TPV 9271-65 (obtained from Advanced Elastomer Systems, Akron,Ohio). Comparative Example 0 was a SEBS copolymer, KRATON™ G2705(obtained from KRATON Polymers LLC, Houston, Tex.). Comparative ExampleP was a SBS copolymer, KRATON® G3202 (obtained from KRATON Polymers LLC,Houston, Tex.).

EXAMPLES 20-26

Example 20 was 100% of Example 19f. Example 21 was similar to Example20, except that 30% of Example 19f was replaced with a high densitypolyethylene (HDPE), DMDA-8007 (from The Dow Chemical Company, Midland,Mich.I). Example 22 was similar to Example 20, except that 20% ofExample 19f was replaced with DMDA-8007. Example 23 was similar toExample 20, except that 10% of Example 19f was replaced with DMDA-8007.Example 24 was similar to Example 20, except that 30% of Example 19f wasreplaced with a homopolymer polypropylene, H700-12 (from The DowChemical Company, Midland, Mich.). Example 25 was similar to Example 20,except that 20% of Example 19f was replaced with H700-12. Example 26 wassimilar to Example 20, except that 10% of Example 19f was replaced withH700-12.

Comparative Examples Q-X

Comparative Example Q was similar to Example 21, except that Example19fwas replaced with a polyolefin elastomer, ENGAGE® ENR 7380 (fromDuPont Dow Elastomers, Wilmington, Del.). Comparative Example R wassimilar to Example 24, except that Example 19f was replaced with ENGAGE®ENR 7380. Comparative Example S was similar to Example 20, except thatExample 19f was replaced with a polyolefin elastomer, ENGAGE® 8407 (fromDuPont Dow Elastomers, Wilmington, Del.) and the sample is 30 mil (0.762mm) thick. Comparative Example T was similar to Example 20, except thatExample 19f was replaced with a polyolefin elastomer, ENGAGE® 8967 (fromDuPont Dow Elastomers, Wilmington, Del.). Comparative Example U wassimilar to Example 24, except that Example 19f was replaced with apropylene-ethylene copolymers, VERSIFY® DE3300 (from The Dow ChemicalCompany, Midland, Mich.). Comparative Example V was similar to Example24, except that Example 19f was replaced with a propylene-ethylenecopolymer, VERSIFY® DE3400 (from The Dow Chemical Company, Midland,Mich.). Comparative Example W was similar to Example 22, except thatExample 19f was replaced with VERSIFY® DE3300. Comparative Example X wassimilar to Example 322 except that Example 19f was replaced withVERSIFY® DE3400.

EXAMPLES 27-33

Example 27 was a mixture of 56% of Example 19f, 16% of H700-12, and 28%of RENOIL® 625 (an oil from Renkert Oil Elversony, Pa.). Example 28 wassimilar to Example 27, except that the mixture was 33% of Example 19f,17% of H700-12, and 50% of RENOIL® 625. Example 29 was similar toExample 27, except that the mixture was 56% of Example 19f, 16% ofDMDA-8007, and 28% of RENOIL® 625. Example 30 was similar to Example 27,except that the mixture was 33% of Example 19f, 17% of DMDA-8007, and50% of RENOIL® 625. Example 31 was similar to Example 27, except thatthe mixture was 17% of Example 19f, 16% of H700-12, 16% of KRATON® G2705and 50% of RENOIL® 625. Example 32 was similar to Example 20, exceptthat 1% of AMPACET® 10090 (an Erucamide concentrate from AmpacetCorporation, Tarrytown, N.Y.), was added as the slip/anti-blockingagent. Example 33 was similar to Example 32, except that 5% of AMPACET®10090 was added as the slip/anti-blocking agent.

Mechanical and Physical Properties Measurements

The Thermomechanical (TMA) properties, hardness, compression setproperties, flexural modulus, gull wing tear strength, Vicat softeningpoint, blocking property, scratch mar resistance, ultimate elongation,100% modulus, 300% modulus, ultimate tensile strength, and yieldstrength of Comparative Examples L-X and Examples 20-33 were measuredand the results are shown in Tables 13 and 14 below.

The penetration temperature by thermal mechanical analysis (TMA)technique was conducted on 30 mm diameter x 3.3 mm thick, compressionmolded discs, formed at 180° C. and 10 MPa molding pressure for 5minutes and then air quenched. The instrument used was a Perkin-ElmerTMA 7. In the TMA test, a probe with 1.5 mm radius tip (P/N N519-0416)was applied to the surface of the sample disc with 1N force. Thetemperature was raised at 5° C./minute from 25° C. The probe penetrationdistance was measured as a function of temperature. The experiment endedwhen the probe had penetrated 0.1 mm and 1 mm respectively into thesample. The 0.1 mm and 1 mm penetration temperatures of each example arelisted in Table 13 below.

The Shore D hardness of each sample was measured according to ASTM D2240, which is incorporated herein by reference.

The compression set properties of each sample at 23° C. and 70° C. weremeasured according to ASTM D 4703, which is incorporated herein byreference.

The flexural modulus of each sample was measured according to the methoddescribed in ASTM D 790, which is incorporated herein by reference.

The gull wing tear strength of each sample was measured according to themethod described in ASTM D 1004, which is incorporated herein byreference.

The Vicat softening point of each sample was measured according to themethod described in ASTM D1525, which is incorporated herein byreference.

The blocking of each sample was measured by stacking six each4″×4″×0.125″ injection molded plaques, leaving the plaques at ambientconditions (73 F) for 24 hours, then un-stacking the plaques. Theblocking rating is between I and 5 with 5 being excellent (all theplaques easily un-stacked) to 1 being unacceptable (where the 6 plaqueshad adhered to each other so much that none of the plaques could beseparated by hand).

The scratch mar resistance of each sample was measured by manuallyscribing an X on a 4×4×0.125 inch plaque from corner to corner with arounded plastic stylus. The scratch mar resistance rating is between1and 5 with 5 is excellent (where no evidence of the X is visible) and 1is unacceptable (where the X is highly visible and can not be rubbedoff).

The 100% modulus, 300% modulus, ultimate tensile strength, ultimateelongation, and yield strength of each sample were measured according toASTM D 412, which is incorporated herein by reference. TABLE 13 0.1 mm1.0 mm Compression Compression Flexural Tear Vicat TMA TMA Set at Set atModulus Strength Softening Scratch Mar Sample (° C.) (° C.) Shore D 70°C. 23° C. (psi) (lbs/in) Point (° C.) Blocking Resistance Comp. Ex. L 49129 53 67 49 26654 391 69 5 4 Comp. Ex. M 25 78 10 91 17  1525 / 58 5 4Comp. Ex. N 60 146 15 51 30  4613 149 65 4 4 Comp. Ex. O 71 137 / 40 21 2781 169 / 3 1 Comp. Ex. P 53 71 / 106  15  2043 149 / 1 1 Example 2067 99 17 57 21  4256 206 44 1 1 Example 21 94 111 34 55 43 22071 441 661 1 Example 22 98 113 33 56 31 14261 323 59 1 1 Example 23 74 103 25 5228  6943 254 50 1 1 Example 24 99 111 36 66 37 24667 421 67 1 1 Example25 84 104 30 61 29 12325 331 55 1 1 Example 26 81 104 24 61 23 / 257 471 1 Comp. Ex. Q 101 119 41 63 10 21358 426 59 1 1 Comp. Ex. R 101 146 4197 27 20267 / 58 3 3 Comp. Ex. S 35 52 16 112  35  2116 186 / 1 1 Comp.Ex. T 48 95 22 83 37  6475 234 / 2 1 Comp. Ex. U 116 142 40 / / / / / 34 Comp. Ex. V 53 113 33 / / 21348 / / 1 3 Comp. Ex. W 68 95 33 76 4411497 328 / 2 3 Comp. Ex. X 40 64 25 87 40 11384 281 / 1 1 Example 27 76105 18 48 28 / 252 / 2 1 Example 28 49 95 13 57 27 / 177 / 2 2 Example29 63 106 18 42 30 / 215 47 2 1 Example 30 54 99 10 / / / / 48 2 2Example 31 48 99 12 55 41 / / 57 3 2 Example 32 69 99 20 54 21 / / 44 54 Example 33 74 99 19 52 19 / / 44 5 5

TABLE 14 Ultimate 100% 300% Tensile Ultimate Yield Modulus ModulusStrength Elongation Strength Sample (psi) (psi) (psi) (%) (psi) Comp.Ex. L 1934 0 2522 224 607 Comp. Ex. M 198 140 549 505 45 Comp. Ex. N 336175 604 459 122 Comp. Ex. O 213 118 1038 656 82 Comp. Ex. P 613 0 563 97253 Example 20 333 130 672 1039 162 Example 21 795 258 1430 1007 652Example 22 589 198 1062 1026 443

Comparative Examples L, M, N, 0 and P are commercial flexible moldedgoods resins which are not olefin-based. Examples 20-26 are variousembodiments of the olefin block copolymer (as a base resin or as a blendof the base resin with PP and/or HDPE) demonstrating the improvedbalance of low modulus and high upper service temperature. ComparativeExamples Q-X are commercial flexible molded good resins that are olefm-based. Examples 20-26 demonstrate the improved balance of low modulusand high upper service temperature over Comparative Examples Q-X.

SEBS/Inventive Interpolymer Blends

Blends of ethylene/α-olefin block copolymer and hydrogenated styrenicsblock copolymer (OBC/SEBS) were prepared using a Haake Rheomix 300rheometer. The temperature of the sample bowl was set at 190° C. and therotor speed was 40 rpm. After all the components were added, the mixingwas continued for about five minutes or until a stable torque has beenestablished. Samples for further testing and evaluation were compressionmolded a Garver automatic press at 190° C. under 44.45 kN force for 3minutes. The molten materials were subsequently quenched with the pressequilibrated at room temperature using an electronic cooling bath.

Comparative Examples Y1-Y5

Comparative Example Y1 was 100% of KRATON® G61652, astyrene-ethylene/butylenes-styrene block copolymer available from KRATONPolymers LLC, Houston, Tex. Comparative Example Yl was the same asComparative Example J*. Comparative Example Y2 was a blend of 75% ofKRATON® G1652 and 25% of AFFINITY® EG8100. Comparative Example Y3 was ablend of 50% of KRATON® G1652 and 50% of AFFINITY® EG8100. ComparativeExample Y4 was a blend of 25% of KRATON®G1652 and 75% of AFFINITY®EG8100. Comparative Example Y5 was 100% AFFINITY® EG8100. ComparativeExample Y5 was the same as Comparative Example H*.

EXAMPLES 34-45

Example 34 was a blend of 75% of KRATON® G1652 and 25% of Example orPolymer 19a. Example 35 was a blend of 50% of KRATON® G1652 and 50% ofExample 19a. Example 36 was a blend of 25% of KRATON® G1652 and 75% ofExample 19a. Example 37 was the same as Example 19a. Example 38 was ablend of 75% of KRATON® G1652 and 25% of Example 19b. Example 39 was ablend of 50% of KRATON® G1652 and 50% of Example 19b. Example 40 was ablend of 25% of KRATON® G1652 and 75% of Example 19b. Example 41 was thesame as Example 19b. Example 42 was a blend of 75% of KRATON® G1652 and25% of Polymer 19i. Polymer 19i was an interpolymer preparedsubstantially similarly to Examples 1-19 and Example 19a-1 9h. Oneskilled in the art would know how to manipulate process conditions, suchas shuttling agent ratios, hydrogen flow, monomer concentration, etc.,to make a target polymer using the process conditions already detailedin the instant application. Example 43 was a blend of 50% of KRATON®G1652 and 50% of Polymer 19i. Example 44 was a blend of 25% of KRATON®GI1652 and 75% of Polymer 19i. Example 45 was 100% of Polymer 19i.

Mechanical and Physical Properties Measurement

The thermomechanical (TMA) properties, elastic recovery at 300% strain,elongation at break, tensile strength and Elmendorf tear strength ofcomparative examples Y1-Y5 and Examples 34-45 were measured by methodsdescribed herein and known to one of skill in the art and the resultsare shown in Table 15 below. TABLE 15 Compositions and properties ofSEBS blends of Examples 34-45 and Comparative Examples Y1-Y5. TMAElastic Elongation Tensile Component Temperature Recovery @ BreakStrength Elmendorf tear B content, % Component B² (° C.)¹ @ 300% strain(%) (MPa) (g/mil) Comparative Example Y1 0 AFFINITY ® EG8100³ 97 92589.8 21.2 70.2 Comparative Example Y2 25 AFFINITY ® EG8100 86 90 675.823.82 81.04 Comparative Example Y3 50 AFFINITY ® EG8100 71 82 664.317.08 47.57 Comparative Example Y4 75 AFFINITY ® EG8100 63.3 73 746.517.44 43.16 Comparative Example Y5 100 AFFINITY ® EG8100 60.2 61.7 777.413.52 55.6 Example 34 25 19a⁴ 100 92 742.4 28.46 50.71 Example 35 50 19a103 89 763.3 18.75 51.02 Example 36 75 19a 106 83.7 827.9 17.77 56.89Example 37 100 19a 107.2 78.3 986.4 13.63 204.3 Example 38 25 19b⁵ 99.592.7 693.6 24.45 41.27 Example 39 50 19b 101 90 770.8 21.1 36.05 Example40 75 19b 104.9 86 813.1 18.18 34.7 Example 41 100 19b 106 80 931.513.93 67.76 Example 42 25 19i⁶ 100 93.3 672 22.13 47.11 Example 43 5019i 102.5 91 704.1 15.62 34.76 Example 44 75 19i 103.7 88 1059 18.4220.85 Example 45 100 19i 108 80.2 1518 13.3 39.5Notes:¹TMA temperature was measured at 1 mm penetration with a heating rate of5° C./min under 1N force.²The rest is Component A which is KRATON ® G1652, a SEBS available fromKRATON Polymers LLC.³AFFINITY ® EG8100 is a substantially linear ethylene/1-octene copolymerhaving I₂ of 1 g/10 min. (ASTM D-1238) and density of 0.870 g/cc (ASTMD-792).⁴19a is an inventive ethylene/octene copolymer having I₂ of 1 g/10 min.and density of 0.878 g/cc.⁵19b is an inventive ethylene/octene copolymer having I₂ of 1 g/10 min.and density of 0.875 g/cc.⁶19i is an inventive ethylene/butene copolymer having I₂ of 1 g/10 min.and density of 0.876 g/cc.

Elastic recovery properties of exemplary blends (i.e., Examples 34-45)and Comparative Examples Y1-Y5 at various amounts of SEBS (i.e., KRATON®G1652) in the blend are shown in FIG. 13. The TMA temperatures ofexemplary blends and Comparative Examples Y1-Y5 at various amounts ofSEBS in the blend are shown in FIG. 14. As seen in Table 15 and FIGS.13-14, the exemplary blends (i.e., Examples 34-45) exhibit improved heatresistance and elastic recovery properties over the correspondingComparative Examples Y1-Y5.

ADDITIONAL EXAMPLES EXAMPLES 46-49

Examples 46-49 were prepared in a similar fashion as Examples 19A-Jabove. Table 16 gives the polymerization conditions for the preparationof these examples, Table 17 gives physical property information forthese polymers and Table 18 gives hard and soft segment data for thesepolymers. TABLE 16 Polymerization Conditions Cat Cat A1 Cat B2 DEZ CocatCocat Poly C₈H₁₆ Solv. T A1² Flow B2³ Flow DEZ Flow Conc. Flow [C₂H₄]/Rate⁵ Conv Ex. kg/hr kg/hr H₂ sccm¹ ° C. ppm kg/hr ppm kg/hr Conc %kg/hr ppm kg/hr [DEZ]⁴ kg/hr 6% Solids % Eff.⁷ 46 107 1105 900 120 5752.07 100 0.93 5 1.14 5700 1.88 730 234 88% 17.5 182 47 81.8 343.9 2131120 358.97 0.94 298.9 0.18 4.99 0.49 5751.6 0.62 1.96 84.5 91% 17.6214.9 48 105 1107 897 120 575 1.7 100 0.67 5 0.81 5700 1.52 1312 238 88%18 228 49 117 1091 1734 120 568 1.45 100 1.02 5 1.15 5535 1.46 1047 24788% 18.4 266¹standard cm³/min²[N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafniumdimethyl³bis-(1-(2-methylcyclohexyl)ethyl)(2-oxoyl-3,5-di(t-butyl)phenyl)immino)zirconium dimethyl⁴ppm in final product calculated by mass balance⁵polymer production rate⁶weight percent ethylene conversion in reactor⁷efficiency, kg polymer/g M where g M = g Hf + g Z

TABLE 17 Polymer Physical Properties Heat of Density Mw Mn Fusion T_(m)T_(c) T_(CRYSTAF) Tm − T_(CRYSTAF) CRYSTAF Peak Ex. (g/cm³) I₂ I₁₀I₁₀/I₂ (g/mol) (g/mol) Mw/Mn (J/g) (° C.) (° C.) (° C.) (° C.) Area(percent) 46 0.866 5.2 36.3 7 89500 45300 2.0 25 119 97 n/a n/a n/a 470.867 10.1 71.1 7 71200 32200 2.2 33 117 98 n/a n/a n/a 48 0.866 0.9 0.07.3 134900 63300 2.1 22 119 98 n/a n/a n/a 49 0.873 10.1 0.0 7.6 7800039100 2.0 35.59 119.4 102.2 n/a n/a n/an/a: denotes not available.

TABLE 18 Hard and Soft Segment Data for Polymers 46-49 wt % wt % octenein wt % Soft Hard Soft Example Segment Segment Segment 46 0.855 15 85 470.855 15 85 48 0.855 15 85 49 0.853 30 70

EXAMPLES 50-109

Tables 19 and 20 give physical information on the styrenic blockcopolymers used in Examples 50-109, which are examples of blendcompositions of the present invention. Compositions and tensileproperties of these blends are given in Table 21. TABLE 19 StyrenicBlock Copolymers G1657 G1652 Parameter Units Test Method linear SEBStriblock linear SEBS triblock Polystyrene content weight % BAM 91912.3-14.3 29.0-30.8 Solution viscosity[a] cps BAM 922 1,200-1,800400-525 Styrene/Rubber ratio % 13/87 30/70 Diblock content % 30 <1 Meltindex gms/10 min 230° C., 5 kg 22 5 Specific gravity g/cm3 0.89 0.91Shore A (10 s)[b] 47 69 Tensile strength MPa [c] 900 600 Elongation %[c] 13.9 22 2% Secant Modulus MPa [c] 3.9 19 Permanent Set % [d] 22 16[a] 20% w toluene solution at 25° C.[b] Typical values on polymer compression molded at about 150° C. (300°F.)[c] Tensile Test at Ambient Conditions (see description in thisdocument)[d] 300% Hysteresis Test at Ambient Conditions (see description in thisdocument)

TABLE 20 Additional Styrenic Block Copolymers Test VECTOR 4111 VECTOR4211 Parameter Units Method linear SIS triblock linear SIS triblockStyrene weight % 18 30 Diblock Content weight % <1.0 <1.0 MFR(1) g/10min ASTM D-1238 12 13 Specific Gravity g/cm3 ASTM D-792 0.93 0.94Tensile Strength MPa (2.3) 16.0 22.0 Elongation % (2.3) 1300 1174 2%Secant Modulus MPa (2.3) 1.6 4.6 Permanent Set % (2.4) 9 8(1) Condition G (200° C., 5 kg)(2) Typical values on compression molded plaques(3) Tensile Test at Ambient Conditions (see description in thisdocument)(4) 300% Hysteresis Test at Ambient Conditions (see description in thisdocument)

TABLE 21 Blends and Tensile Measurements of Inventive Compositions 2%Sec Elongation Tensile Set after 300% Blend Blend Blend Component 1/ Modat Break Strength Hysteresis Example Component 1 Component 2 BlendComponent 2 (MPa) (i) (%) (i) (MPa) (i) (%) (ii) 50 A1^(a) 47 25/75 3.92100 5.5 0 51 A1^(a) 47 50/50 3.3 1700 3.2 34 52 A1^(a) 47 75/25 1.81000 1.8 35 53 A1^(a) 46 25/75 3.3 2300 4.6 39 54 A1^(a) 46 50/50 1.41700 2.4 37 55 A1^(a) 46 75/25 1.5 1100 1.8 34 56 A1^(a) 48 25/75 4.71400 7.8 36 57 A1^(a) 48 50/50 0.5 400 1.1 32 58 A1^(a) 48 75/25 0.91500 3.8 30 59 A1^(a) 49 25/75 8.1 2200 3.5 42 60 A1^(a) 49 50/50 4.51200 2.0 34 61 A1^(a) 49 75/25 1.4 1200 1.8 30 62 A2^(b) 47 25/75 6.61800 5.0 34 63 A2^(b) 47 50/50 7.6 1500 5.1 28 64 A2^(b) 47 75/25 18.01400 5.9 20 65 A2^(b) 46 25/75 7.3 2200 4.5 36 66 A2^(b) 46 50/50 14.71600 4.2 26 67 A2^(b) 46 75/25 6.6 1200 6.6 19 68 A2^(b) 48 25/75 6.71400 7.8 33 69 A2^(b) 48 50/50 8.5 1000 4.8 22 70 A2^(b) 48 75/25 9.31300 8.8 18 71 A2^(b) 49 25/75 13.9 2000 3.4 39 72 A2^(b) 49 50/50 10.11300 4.3 28 73 A2^(b) 49 75/25 5.5 1500 10.4 18 74 A3^(c) 47 25/75 12.01733 5.0 33 75 A3^(c) 47 50/50 19.3 1115 6.0 24 76 A3^(c) 47 75/25 7.61199 15.1 18 77 A3^(c) 46 25/75 9.5 1922 4.2 34 78 A3^(c) 46 50/50 10.11084 5.5 26 79 A3^(c) 46 75/25 8.3 1212 12.4 21 80 A3^(c) 48 25/75 10.61229 7.7 35 81 A3^(c) 48 50/50 9.5 1128 8.4 25 82 A3^(c) 48 75/25 7.31229 15.6 19 83 A3^(c) 49 25/75 12.8 2108 3.3 48 84 A3^(c) 49 50/50 18.4996 3.1 33 85 A3^(c) 49 75/25 7.9 1158 13.0 21 86 A4^(d) 47 25/75 8.51800 4.7 29 87 A4^(d) 47 50/50 5.4 1100 8.0 26 88 A4^(d) 47 75/25 4.31000 9.9 21 89 A4^(d) 46 25/75 7.0 1900 3.2 29 90 A4^(d) 46 50/50 5.61100 8.4 24 91 A4^(d) 46 75/25 4.3 1000 10.0 22 92 A4^(d) 48 25/75 6.11400 8.2 27 93 A4^(d) 48 50/50 6.3 1200 11.1 25 94 A4^(d) 48 75/25 3.8900 8.4 22 95 A4^(d) 49 25/75 10.2 1000 2.8 36 96 A4^(d) 49 50/50 8.01000 8.4 27 97 A4^(d) 49 75/25 5.0 1000 9.7 24 98 A5^(e) 47 25/75 9.91000 6.9 32 99 A5^(e) 47 50/50 11.9 700 10.2 27 100 A5^(e) 47 75/25 10.9700 17.3 17 101 A5^(e) 46 25/75 7.8 1100 6.0 32 102 A5^(e) 46 50/50 18.3700 11.8 26 103 A5^(e) 46 75/25 45.3 700 20.6 25 104 A5^(e) 48 25/7511.3 900 9.3 29 105 A5^(e) 48 50/50 9.6 800 14.5 19 106 A5^(e) 48 75/2517.3 600 16.6 20 107 A5^(e) 49 25/75 9.1 900 6.3 45 108 A5^(e) 49 50/5029.4 600 9.6 28 109 A5^(e) 49 75/25 22.0 600 15.9 23Notes:^(a)Vector 4111 from Dexco Polymers LP^(b)Vector 4211 from Dexco Polymers LP^(c)Vector 8508 from Dexco Polymers LP^(d)KRATON G1657 from KRATON Polymers LLC^(e)KRATON G1652 from KRATON Polymers LLC(i) Tensile Test at Ambient Conditions (see description in thisdocument)(ii) 300% Hysteresis Test at Ambient Conditions (see description in thisdocument)

Table 22 shows composition and tensile measurements for ternary blendsof an olefin block copolymer, a linear SIS triblock polymer, Vector4111, a linear SEBS triblock polymer, KRATON G1657 and a linear SBStriblock polymer, Vector 8508. TABLE 22 Ternary Blends Immediate BlendBlend Blend Blend Set Compo- Compo- Compo- Compo- Blend Blend ElongationTensile 2% Secant after nent 1 nent 2 nent 3 nent 1 Component 2Component 3 at Strength Modulus 300% Example Resin Resin Resin (%) (%)(%) Break % (i) (MPa) (i) (MPa) (i) Strain (%) (ii) 110 46 A4^(c) A1^(a)45 10 45 1300 4.1 2.9 27 111 46 A4^(c) A3^(b) 45 10 45 1000 5.6 8.2 29112 48 A4^(c) A1^(a) 45 10 45 1100 4.4 3.4 25 113 48 A4^(c) A3^(b) 45 1045 1200 10.8 8.5 25Notes:^(a)Vector 4111 from Dexco Polymers LP^(b)Vector 8508 from Dexco Polymers LP^(c)KRATON G1657 from KRATON Polymers LLC(i) Tensile Test at Ambient Conditions (see description in thisdocument)(ii) 300% Hysteresis Test at Ambient Conditions (see description in thisdocument)

FIG. 14 shows the elastic recovery inventive and comparative exampleswhich comprise SEBS (see table 15). At similar SEBS level, the inventivecompositions exhibit greater recovery compared to the comparativeexamples. Higher recovery is generally recognized as advantaged behaviorin the form of greater elasticity.

FIG. 15 compares the elasticity as measured by permanent set of examplescomprising ethylene x-olefin and SIS. Examples 54 and 57 exhibit 37 and32% permanent set, respectively. Examples 1 10 and 1 12 have the sameproportion of ethylene (X-olefin to SIS but with 10% SEBS in the overallcomposition. These examples exhibit similar permanent set compared toexamples 90 and 93 which comprise ethylene α-olefin and SEBS and no SIS.This result shows the utility of ternary blends. Though not intended tobe limited by theory, it is thought that compatibility is enhanced in aternary blend.

While the invention has been described with respect to a limited numberof embodiments, the specific features of one embodiment should not beattributed to other embodiments of the invention. No single embodimentis representative of all aspects of the invention. In some embodiments,the compositions or methods may include numerous compounds or steps notmentioned herein. In other embodiments, the compositions or methods donot include, or are substantially free of, any compounds or steps notenumerated herein. Variations and modifications from the describedembodiments exist. Finally, any number disclosed herein should beconstrued to mean approximate, regardless of whether the word “about” or“approximately” is used in describing the number. The appended claimsintend to cover all those modifications and variations as falling withinthe scope of the invention.

1. A composition comprising: at least one ethylene/α-olefininterpolyrner, wherein the ethylene/α-olefin interpolymer (a) has aMw/Mn from about 1.7 to about 3.5, at least one melting point, Tm, indegrees Celsius, and a density, d, in grams/cubic centimeter, whereinthe numerical values of Tm and d correspond to the relationship:Tm>−2002.9+4538.5(d) −2422.2(d)²; or (b) has a Mw/Mn from about 1.7 toabout 3.5, and is characterized by a heat of fusion, ΔH in J/g, and adelta quantity, ΔT, in degrees Celsius defined as the temperaturedifference between the tallest DSC peak and the tallest CRYSTAF peak,wherein the numerical values of ΔT and ΔH have the followingrelationships:ΔT>−0.1299(ΔH)+62.81 for ΔH greater than zero and up to 130 J/g,ΔT≧48° C. for ΔH greater than 130 J/g, wherein the CRYSTAF peak isdetermined using at least 5 percent of the cumulative polymer, and ifless than 5 percent of the polymer has an identifiable CRYSTAF peak,then the CRYSTAF temperature is 30° C.; or (c) is characterized by anelastic recovery, Re, in percent at 300 percent strain and 1 cyclemeasured with a compression-molded film of the ethylene/α-olefininterpolymer, and has a density, d, in grams/cubic centimeter, whereinthe numerical values of Re and d satisfy the following relationship whenethylene/α-olefin interpolymer is substantially free of a cross-linkedphase:Re>1481-1629(d); or (d) has a molecular fraction which elutes between40° C. and 130° C. when fractionated using TREF, characterized in thatthe fraction has a molar comonomer content of at least 5 percent higherthan that of a comparable random ethylene interpolymer fraction elutingbetween the same temperatures, wherein said comparable random ethyleneinterpolymer has the same comonomer(s) and has a melt index, density,and molar comonomer content (based on the whole polymer) within 10percent of that of the ethylene/α-olefin interpolymer; or (e) has astorage modulus at 25° C., G′(25° C.), and a storage modulus at 100° C.,G′(100° C.), wherein the ratio of G′(25° C.) to G′(100° C.) is in therange of about 1:1 to about9:1; and, at least one styrenic blockcopolymer, or a combination thereof; wherein the ethylene/α-olefininterpolymer has a density of from about 0.85 to about 0.885 g/cc. 2.The composition of claim 1 wherein the ethylene/α-olefin interpolymerhas a density of from about 0.86 to about 0.885 g/cc.
 3. The compositionof claim 2 further comprising polystyrene-saturatedpolybutadiene-polystyrene.
 4. The composition of claim 1 wherein theethylene/α-olefin interpolymer has a melt index (I₂) of from about 0.5g/10 min. to about 20 g/10 min.
 5. The composition of claim 4 furthercomprising polystyrene-saturated polybutadiene-polystyrene.
 6. Thecomposition of claim 1 wherein the ethylene/α-olefin interpolymner has amelt index (I₂) of from about 0.75 g/10 min. to about 1.5 g/10 min. 7.The composition of claim 1 in the form of a cast film layer, wherein theethylene/α-olefin interpolymer has a melt index (I₂) of from about 3g/10 min. to about 17 g/10 min.
 8. The composition of claim 1 in theform of an extruded laminate, wherein the ethylene/a-olefm interpolymerhas a melt index (I₂) of from about 3 g/10 min. to about 17 g/10 min. 9.The composition of claim 1 in the form of a blown film layer, whereinthe ethylene/α-olefin interpolymer has a melt index (I₂) of from about0.5 g/10 min. to about 5 g/10 min.
 10. The composition of claim 1wherein the ethylene/α-olefin interpolymer is made using a diethyl zincchain shuttling agent.
 11. The composition of claim 9 wherein theethylene/α-olefin interpolymer is made by using a concentration ofdiethyl zinc chain shuttling agent such that the ratio of zinc toethylene is from about 0.03×10⁻³ to about 1.5×10⁻³.
 12. The compositionof claim 1 further comprising polystyrene-saturatedpolybutadiene-polystyrene.
 13. An elastic film layer comprising thecomposition of claim 1 wherein the ethylene/α-olefin interpolymer has adensity of from about 0.85 to about 0.89 g/cc and a melt index (I₂) offrom about 0.5 g/10 min. to about 20 g/10 min. and wherein a compressionmolded film layer is capable of stress relaxation of at most about 60%at 75% strain at 100° F. for at least 10 hours.
 14. A laminatecomprising at least one elastic or inelastic fabric, and an elastic filmlayer comprising the composition of claim
 13. 15. The laminate of claim14 wherein the film layer is capable of stress relaxation of at mostabout 40% at 75% strain at 100° F. for at least 10 hours.
 16. Thelaminate of claim 14 wherein the fabric is nonwoven fabric selected fromthe group consisting of melt blown, spunbond, carded staple fibers,spunlaced staple fibers, and air laid staple fibers.
 17. The laminate ofclaim 14 wherein the fabric comprises at least two compositionallydifferent fibers.
 18. The laminate of claim 14, wherein the fabriccomprises a multi-component polymeric fiber, wherein at least one of thepolymeric components comprises at least a portion of the fiber'ssurface.
 19. A fabricated article comprising the composition of claim 1.20. A fabricated article comprising the elastic film layer of claim 13.21. A fabricated article comprising the laminate of claim
 14. 22. Afabricated article comprising the composition of claim 1 wherein saidfabricated articles is selected from the group consisting of adultincontinence articles, feminine hygiene articles, infant care articles,surgical gowns, medical drapes, household cleaning articles, expandablefood covers, protective clothing and personal care articles.
 23. Afabricated article comprising the elastic film layer of claim 13 whereinsaid fabricated articles is selected from the group consisting of adultincontinence articles, feminine hygiene articles, infant care articles,surgical gowns, medical drapes, household cleaning articles, expandablefood covers, protective clothing and personal care articles.
 24. Afabricated article comprising the laminate of claim 14 wherein saidfabricated articles is selected from the group consisting of adultincontinence articles, feminine hygiene articles, infant care articles,surgical gowns, medical drapes, household cleaning articles, expandablefood covers, protective clothing and personal care articles.
 25. Theelastic film layer of claim 13 in the form of a multilayer filmstructure.
 26. The composition of claim 1 wherein the percent recoveryis greater than or equal to −1629×density (g/cm³)+1481.
 27. Thecomposition of claim 2 wherein the percent recovery is greater than orequal to −1629×density (g/cm³)+1481.
 28. The composition of claim 3wherein the percent recovery is greater than or equal to −1629×density(g/cm³)+1481.
 29. A composition comprising: at least oneethylene/α-olefin interpolymer, wherein the ethylene/α-olefininterpolymer: (a) has a molecular fraction which elutes between 40° C.and 130° C. when fractionated using TREF, characterized in that thefraction has a block index of at least 0.5 and up to about 1 and amolecular weight distribution, Mw/Mn, greater than about 1.3; or (b) hasan average block index greater than zero and up to about 1.0 and amolecular weight distribution, Mw/Mn, greater than about 1.3; and, atleast one styrenic block copolymer; wherein the ethylene/α-olefininterpolymer has a density of from about 0.85 to about 0.885 g/cc. 30.The composition of claim 29 in the form of a cast film layer, whereinthe ethylene/α-olefin interpolymer has a melt index (I₂) of from about0.5g/10 min. to about 20 g/10 min.
 31. The composition of claim 29 inthe form of an extruded laminate, wherein the ethylene/α-olefininterpolymer has a melt index (I₂) of from about 3 g/10 min. to about 17g/10 min.
 32. The composition of claim 29 in the form of a blown filmlayer, wherein the ethylene/α-olefin interpolymer has a melt index (I₂)of from about 0.5 g/10 min. to about 5 g/10 min.
 33. A necked bondedmaterial comprising a laminate comprising the composition of claim 1.34. The necked bonded material of claim 33 wherein the laminate isapertured.
 35. A stretched bonded material comprising a laminatecomprising the composition of claim
 1. 36. The stretched bonded materialof claim 35 wherein the laminate is apertured.
 37. A machine directionactivated material comprising a laminate comprising the composition ofclaim
 1. 38. The machine direction activated material of claim 36wherein the laminate is apertured.
 39. A cross direction activatedmaterial comprising a laminate comprising the composition of claim 1.40. The cross direction activated material of claim 37 wherein thelaminate is apertured.
 41. A machine direction activated and crossdirection activated material comprising a laminate comprising thecomposition of claim
 1. 42. The machine direction activated and crossdirection activated material of claim 41 wherein the laminate isapertured.